TW201546072A - Hetero-cyclic compound and organic light emitting device using the same - Google Patents
Hetero-cyclic compound and organic light emitting device using the same Download PDFInfo
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- TW201546072A TW201546072A TW104115513A TW104115513A TW201546072A TW 201546072 A TW201546072 A TW 201546072A TW 104115513 A TW104115513 A TW 104115513A TW 104115513 A TW104115513 A TW 104115513A TW 201546072 A TW201546072 A TW 201546072A
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- Prior art keywords
- substituted
- group
- polycyclic
- compound
- unsubstituted
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- 150000002391 heterocyclic compounds Chemical class 0.000 title claims abstract description 28
- 150000001875 compounds Chemical class 0.000 claims description 313
- 125000003367 polycyclic group Chemical group 0.000 claims description 98
- 125000002950 monocyclic group Chemical group 0.000 claims description 89
- 125000003118 aryl group Chemical group 0.000 claims description 46
- 125000001072 heteroaryl group Chemical group 0.000 claims description 36
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 claims description 32
- 239000011368 organic material Substances 0.000 claims description 20
- 125000000217 alkyl group Chemical group 0.000 claims description 19
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 19
- 229910052739 hydrogen Inorganic materials 0.000 claims description 17
- 239000001257 hydrogen Substances 0.000 claims description 17
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 14
- 238000002347 injection Methods 0.000 claims description 12
- 239000007924 injection Substances 0.000 claims description 12
- 230000000903 blocking effect Effects 0.000 claims description 10
- 229910052799 carbon Inorganic materials 0.000 claims description 10
- 125000005549 heteroarylene group Chemical group 0.000 claims description 10
- 125000000592 heterocycloalkyl group Chemical group 0.000 claims description 10
- 229910052736 halogen Inorganic materials 0.000 claims description 9
- 150000002367 halogens Chemical class 0.000 claims description 9
- 125000000732 arylene group Chemical group 0.000 claims description 8
- 230000005525 hole transport Effects 0.000 claims description 8
- 229910052717 sulfur Inorganic materials 0.000 claims description 7
- 125000003342 alkenyl group Chemical group 0.000 claims description 5
- 125000000304 alkynyl group Chemical group 0.000 claims description 5
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 5
- 229910052760 oxygen Inorganic materials 0.000 claims description 5
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- 229960000643 adenine Drugs 0.000 claims description 2
- 125000004450 alkenylene group Chemical group 0.000 claims description 2
- 125000002947 alkylene group Chemical group 0.000 claims description 2
- 125000004419 alkynylene group Chemical group 0.000 claims description 2
- 125000006615 aromatic heterocyclic group Chemical group 0.000 claims description 2
- 125000002993 cycloalkylene group Chemical group 0.000 claims description 2
- 125000006588 heterocycloalkylene group Chemical group 0.000 claims description 2
- 125000002029 aromatic hydrocarbon group Chemical group 0.000 claims 1
- 150000002894 organic compounds Chemical class 0.000 abstract description 2
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 186
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- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 32
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- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 25
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- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 18
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 17
- 238000006467 substitution reaction Methods 0.000 description 15
- 239000010949 copper Substances 0.000 description 14
- UZVGSSNIUNSOFA-UHFFFAOYSA-N dibenzofuran-1-carboxylic acid Chemical compound O1C2=CC=CC=C2C2=C1C=CC=C2C(=O)O UZVGSSNIUNSOFA-UHFFFAOYSA-N 0.000 description 12
- 238000004821 distillation Methods 0.000 description 12
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- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 description 12
- 125000004432 carbon atom Chemical group C* 0.000 description 11
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- XEZNGIUYQVAUSS-UHFFFAOYSA-N 18-crown-6 Chemical compound C1COCCOCCOCCOCCOCCO1 XEZNGIUYQVAUSS-UHFFFAOYSA-N 0.000 description 10
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- 235000019341 magnesium sulphate Nutrition 0.000 description 10
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- VFUDMQLBKNMONU-UHFFFAOYSA-N 9-[4-(4-carbazol-9-ylphenyl)phenyl]carbazole Chemical group C12=CC=CC=C2C2=CC=CC=C2N1C1=CC=C(C=2C=CC(=CC=2)N2C3=CC=CC=C3C3=CC=CC=C32)C=C1 VFUDMQLBKNMONU-UHFFFAOYSA-N 0.000 description 8
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 8
- 150000001412 amines Chemical class 0.000 description 8
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 8
- 125000004122 cyclic group Chemical group 0.000 description 8
- FFYZMBQLAYDJIG-UHFFFAOYSA-N dibenzofuran-2-amine Chemical compound C1=CC=C2C3=CC(N)=CC=C3OC2=C1 FFYZMBQLAYDJIG-UHFFFAOYSA-N 0.000 description 8
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 8
- 125000004076 pyridyl group Chemical group 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 8
- YJTKZCDBKVTVBY-UHFFFAOYSA-N 1,3-Diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=CC(C=2C=CC=CC=2)=C1 YJTKZCDBKVTVBY-UHFFFAOYSA-N 0.000 description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 7
- 125000004093 cyano group Chemical group *C#N 0.000 description 7
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- 238000002474 experimental method Methods 0.000 description 5
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- HIGJBIVBPHAUNA-UHFFFAOYSA-N 2,4-diphenyl-6-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1,3,5-triazine Chemical compound O1C(C)(C)C(C)(C)OB1C1=NC(C=2C=CC=CC=2)=NC(C=2C=CC=CC=2)=N1 HIGJBIVBPHAUNA-UHFFFAOYSA-N 0.000 description 3
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- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 2
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- XGRJZXREYAXTGV-UHFFFAOYSA-N chlorodiphenylphosphine Chemical compound C=1C=CC=CC=1P(Cl)C1=CC=CC=C1 XGRJZXREYAXTGV-UHFFFAOYSA-N 0.000 description 2
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- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 125000003548 sec-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- PJANXHGTPQOBST-UHFFFAOYSA-N stilbene Chemical class C=1C=CC=CC=1C=CC1=CC=CC=C1 PJANXHGTPQOBST-UHFFFAOYSA-N 0.000 description 1
- 125000003011 styrenyl group Chemical group [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000001973 tert-pentyl group Chemical group [H]C([H])([H])C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000001935 tetracenyl group Chemical group C1(=CC=CC2=CC3=CC4=CC=CC=C4C=C3C=C12)* 0.000 description 1
- 125000005247 tetrazinyl group Chemical group N1=NN=NC(=C1)* 0.000 description 1
- 125000003831 tetrazolyl group Chemical group 0.000 description 1
- 238000002207 thermal evaporation Methods 0.000 description 1
- 125000001113 thiadiazolyl group Chemical group 0.000 description 1
- 125000004305 thiazinyl group Chemical group S1NC(=CC=C1)* 0.000 description 1
- 125000000335 thiazolyl group Chemical group 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- 229930192474 thiophene Natural products 0.000 description 1
- 125000001425 triazolyl group Chemical group 0.000 description 1
- DMTNYYLGEBSTEJ-UHFFFAOYSA-N triphenylene-1,2-diamine Chemical class C1=CC=C2C3=C(N)C(N)=CC=C3C3=CC=CC=C3C2=C1 DMTNYYLGEBSTEJ-UHFFFAOYSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
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Abstract
Description
本申請案主張向韓國專利局於2014年5月15日所申請之韓國專利申請案第10-2014-0058651號及第10-2014-0058654號之優先權，其揭示內容在此均併入本發明以供參考。The present application claims priority to Korean Patent Application No. 10-2014-0058651 and No. 10-2014-005865, filed on May 15, 2014, the disclosure of The invention is for reference.
本發明係關於一種雜環化合物及使用其之有機發光裝置。The present invention relates to a heterocyclic compound and an organic light-emitting device using the same.
電致發光裝置是一種自發光型顯示裝置，且具有廣視角、優異對比性及高反應速度之優點。The electroluminescence device is a self-luminous display device and has the advantages of wide viewing angle, excellent contrast, and high reaction speed.
有機發光裝置具有一有機薄膜係設於兩電極之間的結構。當對具有該結構之有機發光裝置施加電壓時，由兩電極注入之電子和電洞於有機薄膜中結合以形成電子電洞對，然後被激發發出光線。有機薄膜可視需要而由單層或多層組成。The organic light-emitting device has a structure in which an organic thin film is provided between the electrodes. When a voltage is applied to the organic light-emitting device having the structure, electrons and holes injected from the two electrodes are combined in the organic film to form an electron hole pair, which is then excited to emit light. The organic film may be composed of a single layer or a plurality of layers as needed.
若有需要，有機薄膜的材料可具有發光功能，例如：亦可使用能夠單獨組成發光層的化合物、或者亦可使用可作為主體-摻體類發光層中的主體或摻體的化合物作為有機薄膜的材料。此外，亦可使用可執行如電洞注入、電洞傳輸、電子阻擋、電洞阻擋、電子傳輸或電子注入功能的化合物作為有機薄膜的材料。If necessary, the material of the organic thin film may have a light-emitting function, for example, a compound capable of constituting the light-emitting layer alone or a compound which can be used as a host or a blend in the host-blend-based light-emitting layer may be used as the organic thin film. s material. Further, a compound which can perform functions such as hole injection, hole transport, electron blocking, hole blocking, electron transport, or electron injection can also be used as the material of the organic thin film.
為了提升有機發光裝置的性能、使用壽命或效能，對於有機薄膜材料之研發持續具有需求。In order to improve the performance, service life or performance of organic light-emitting devices, there is a continuing demand for the development of organic thin film materials.
研究有機發光裝置包含的化合物的化學結構是必需的，該化合物可滿足有機發光裝置所需的材料條件，例如適當的能階、電化學穩定性、熱穩定性等，且根據取代基可執行多種有機發光裝置所需功能。It is necessary to study the chemical structure of the compound contained in the organic light-emitting device, and the compound can satisfy the material conditions required for the organic light-emitting device, such as appropriate energy level, electrochemical stability, thermal stability, etc., and can perform various kinds according to the substituent. The desired function of the organic light-emitting device.
本發明之一實施態樣係提供一種雜環化合物，由下式1所示： [式1]於式1中， R1至R8係互相相同或不同，且各自獨立選自由：氫；氘；鹵素基；-CN；經取代或未經取代之直鏈或支鏈C1 至C60 烷基；經取代或未經取代之直鏈或支鏈C2 至C60 烯基；經取代或未經取代之直鏈或支鏈C2 至C60 炔基；經取代或未經取代之單環或多環C3 至C60 環烷基；經取代或未經取代之單環或多環C2 至C60 雜環烷基；經取代或未經取代之單環或多環C6 至C60 芳基；經取代或未經取代之單環或多環C2 至C60 雜芳基；-SiRR’R”； -P(=O)RR’；及–NRR’所組成之群組；以及 R、R’、及R” 係互相相同或不同，且各自獨立選自由：氫；氘；經取代或未經取代之直鏈或支鏈C1 至C60 烷基；經取代或未經取代之單環或多環C3 至C60 環烷基；經取代或未經取代之單環或多環C6 至C60 芳基；及經取代或未經取代之單環或多環C2 至C60 雜芳基所組成之群組。An embodiment of the present invention provides a heterocyclic compound represented by the following formula 1: [Formula 1] In Formula 1, R1 to R8 are the same or different from each other, and are each independently selected from: hydrogen; hydrazine; halogen; -CN; substituted or unsubstituted linear or branched C 1 to C 60 alkyl; Substituted or unsubstituted linear or branched C 2 to C 60 alkenyl; substituted or unsubstituted linear or branched C 2 to C 60 alkynyl; substituted or unsubstituted monocyclic or Polycyclic C 3 to C 60 cycloalkyl; substituted or unsubstituted monocyclic or polycyclic C 2 to C 60 heterocycloalkyl; substituted or unsubstituted monocyclic or polycyclic C 6 to C 60 a group of aryl; substituted or unsubstituted monocyclic or polycyclic C 2 to C 60 heteroaryl; -SiRR'R";-P(=O)RR'; and -NRR'; R, R', and R" are the same or different from each other, and are each independently selected from: hydrogen; hydrazine; substituted or unsubstituted linear or branched C 1 to C 60 alkyl; substituted or unsubstituted Monocyclic or polycyclic C 3 to C 60 cycloalkyl; substituted or unsubstituted monocyclic or polycyclic C 6 to C 60 aryl; and substituted or unsubstituted monocyclic or polycyclic C 2 A group consisting of C 60 heteroaryl groups.
此外，本發明提供一種有機發光裝置，包括：一正極；一負極；以及一或多層有機材料層，設於該正極與該負極之間；其中該一或多層有機材料層包括如式1所示之雜環化合物。In addition, the present invention provides an organic light-emitting device comprising: a positive electrode; a negative electrode; and one or more organic material layers disposed between the positive electrode and the negative electrode; wherein the one or more organic material layers include the formula 1 Heterocyclic compound.
根據本發明實施態樣之雜環化合物可作為有機發光裝置中之有機材料層之材料。該雜環化合物可作為有機發光裝置中的電洞注入材料、電洞傳輸材料、發光材料、電洞阻擋材料、電子傳輸材料、電子注入材料等。The heterocyclic compound according to an embodiment of the present invention can be used as a material of an organic material layer in an organic light-emitting device. The heterocyclic compound can be used as a hole injecting material, a hole transporting material, a light emitting material, a hole blocking material, an electron transporting material, an electron injecting material, or the like in an organic light-emitting device.
尤其，式1所示之雜環化合物可作為有機發光裝置中的電子注入及/或傳輸層之材料。In particular, the heterocyclic compound represented by Formula 1 can be used as a material of an electron injecting and/or transporting layer in an organic light-emitting device.
此外，式1所示之雜環化合物可作為有機發光裝置中的電洞阻擋層之材料。Further, the heterocyclic compound represented by Formula 1 can be used as a material for the hole blocking layer in the organic light-emitting device.
再者，式1所示之雜環化合物可作為有機發光裝置中的發光層之材料。Further, the heterocyclic compound represented by Formula 1 can be used as a material of the light-emitting layer in the organic light-emitting device.
接著，將詳述本發明。Next, the present invention will be described in detail.
根據本發明實施例之雜環化合物係由式1所示。詳述之，式1所示之雜環化合物因核心結構和取代基之結構特性，故可作為有機發光裝置中之有機材料層材料。The heterocyclic compound according to an embodiment of the present invention is represented by Formula 1. In detail, the heterocyclic compound represented by Formula 1 can be used as an organic material layer material in an organic light-emitting device because of its core structure and structural characteristics of the substituent.
在本發明中，下方將更加詳述式1之取代基。In the present invention, the substituent of Formula 1 will be described in more detail below.
在本發明中，「經取代或未經取代」表示未經取代或經由一個以上的取代基取代，該一個以上的取代基係選自由：氘；鹵素；-CN；直鏈或支鏈C1 至C60 烷基；直鏈或支鏈C2 至C60 烯基；直鏈或支鏈C2 至C60 炔基；單環或多環C3 至C60 環烷基；單環或多環C2 至C60 雜環烷基；單環或多環C6 至C60 芳基；單環或多環C2 至C60 雜芳基；-SiRR’R”； -P(=O)RR’；及–NRR’所組成之群組。或者，「經取代或未經取代」表示未經取代或經由上述取代基中兩個以上取代基鍵結的取代基所取代，或表示未經取代或經上述取代基中兩個以上取代基連結的取代基所取代。例如：「兩個以上取代基連結的取代基」可為聯苯基。換言之，聯苯基亦可為芳基、且可解釋為兩苯基連結的取代基。R、R’、及R” 係互相相同或不同，且各自獨立選自由：氫；氘；鹵素；-CN；直鏈或支鏈C1 至C60 烷基；單環或多環C3 至C60 環烷基；單環或多環C6 至C60 芳基；及單環或多環C2 至C60 雜芳基所組成之群組。該些取代基亦可再被取代。In the present invention, "substituted or unsubstituted" means unsubstituted or substituted by one or more substituents selected from: hydrazine; halogen; -CN; linear or branched C 1 To a C 60 alkyl group; a linear or branched C 2 to C 60 alkenyl group; a linear or branched C 2 to C 60 alkynyl group; a monocyclic or polycyclic C 3 to C 60 cycloalkyl group; a single ring or more Ring C 2 to C 60 heterocycloalkyl; monocyclic or polycyclic C 6 to C 60 aryl; monocyclic or polycyclic C 2 to C 60 heteroaryl; -SiRR'R"; -P(=O) a group consisting of RR'; and -NRR'. Alternatively, "substituted or unsubstituted" means unsubstituted or substituted with a substituent bonded by two or more substituents of the above substituents, or Substituted or substituted with a substituent in which two or more substituents of the above substituent are bonded. For example, "a substituent in which two or more substituents are bonded" may be a biphenyl group. In other words, the biphenyl group may also be an aryl group and may be interpreted as a substituent in which two phenyl groups are bonded. R, R', and R" are the same or different from each other, and are each independently selected from: hydrogen; hydrazine; halogen; -CN; linear or branched C 1 to C 60 alkyl; monocyclic or polycyclic C 3 to a group consisting of a C 60 cycloalkyl group; a monocyclic or polycyclic C 6 to C 60 aryl group; and a monocyclic or polycyclic C 2 to C 60 heteroaryl group. These substituents may also be substituted.
「取代」一詞表示化合物中鍵結至碳原子之氫原子變成另一取代基，且被取代的位置並無限制，只要該位置的氫原子被取代即可，即取代基可被取代的位置，而當兩個以上被取代時，兩個以上的取代基可為互相相同或不同。The term "substituted" means that the hydrogen atom bonded to the carbon atom in the compound becomes another substituent, and the position of the substitution is not limited as long as the hydrogen atom at the position is substituted, that is, the position at which the substituent can be substituted. And when two or more are substituted, two or more substituents may be the same or different from each other.
在本發明中，鹵素可為：氟、氯、溴或碘。In the present invention, the halogen may be: fluorine, chlorine, bromine or iodine.
在本發明中，烷基包括具有1至60個碳原子之直鏈或支鏈，且可額外經由另一取代基所取代。烷基的碳原子數可為1至60，較佳為1至40，再更佳為1至20。具體的範例包含甲基、乙基、丙基、正丙基、異丙基、丁基、正丁基、異丁基、叔丁基、仲丁基、1-甲基-丁基、1-乙基-丁基、戊基、正戊基、異戊基、新戊基、叔戊基、己基、正己基、1-甲基戊基、2-甲基戊基、4-甲基-2-戊基、3,3-二甲基丁基、2-乙基丁基、庚基、正庚基、1-甲基己基、環戊基甲基、環己基甲基、辛基、正辛基、叔辛基、1-甲基庚基、2-乙基己基、2-丙基戊基、正壬基、2,2-二甲基庚基、1-乙基丙基、1,1-二甲基丙基、異己基、2-甲基戊基、4-甲基己基、5-甲基己基等，但本發明不限於此。In the present invention, the alkyl group includes a straight chain or a branched chain having 1 to 60 carbon atoms, and may be additionally substituted with another substituent. The alkyl group may have a carbon number of from 1 to 60, preferably from 1 to 40, still more preferably from 1 to 20. Specific examples include methyl, ethyl, propyl, n-propyl, isopropyl, butyl, n-butyl, isobutyl, tert-butyl, sec-butyl, 1-methyl-butyl, 1- Ethyl-butyl, pentyl, n-pentyl, isopentyl, neopentyl, tert-amyl, hexyl, n-hexyl, 1-methylpentyl, 2-methylpentyl, 4-methyl-2 -pentyl, 3,3-dimethylbutyl, 2-ethylbutyl, heptyl, n-heptyl, 1-methylhexyl, cyclopentylmethyl, cyclohexylmethyl, octyl, n-octyl Base, tert-octyl, 1-methylheptyl, 2-ethylhexyl, 2-propylpentyl, n-decyl, 2,2-dimethylheptyl, 1-ethylpropyl, 1,1 - dimethylpropyl, isohexyl, 2-methylpentyl, 4-methylhexyl, 5-methylhexyl, etc., but the invention is not limited thereto.
在本發明中，烯基包括具有2至60個碳原子之直鏈或支鏈，且可額外經由另一取代基所取代。烯基的碳原子數可為2至60，較佳為2至40，再更佳為2至20。具體的範例包含乙烯基、1-丙烯基、異丙烯基、1-丁烯基、2-丁烯基、3-丁烯基、1-戊烯基、2-戊烯基、3-戊烯基、3-甲基-1-丁烯基、1,3-丁二烯基、丙烯基、1-苯基乙烯基-1-基、2-苯基乙烯基-1-基、2,2-二苯基乙烯基-1-基、2-苯基-2-（萘基-1-基）乙烯基-1-基、2,2-雙（二苯基-1-基）乙烯基-1-基、芪基(stilbenyl group)、苯乙烯基(styrenyl group)等，但本發明不限於此。In the present invention, an alkenyl group includes a straight chain or a branched chain having 2 to 60 carbon atoms, and may be additionally substituted with another substituent. The alkenyl group may have a carbon number of from 2 to 60, preferably from 2 to 40, still more preferably from 2 to 20. Specific examples include vinyl, 1-propenyl, isopropenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-pentenyl, 2-pentenyl, 3-pentene , 3-methyl-1-butenyl, 1,3-butadienyl, propenyl, 1-phenylvinyl-1-yl, 2-phenylvinyl-1-yl, 2,2 -diphenylvinyl-1-yl, 2-phenyl-2-(naphthyl-1-yl)vinyl-1-yl, 2,2-bis(diphenyl-1-yl)vinyl- 1-base, stilbenyl group, styrenyl group, etc., but the invention is not limited thereto.
在本發明中，炔基包括具有2至60個碳原子之直鏈或支鏈，且可額外經由另一取代基所取代。炔基的碳原子數可為2至60，較佳為2至40，再更佳為2至20。In the present invention, an alkynyl group includes a straight chain or a branched chain having 2 to 60 carbon atoms, and may be additionally substituted with another substituent. The alkynyl group may have a carbon number of from 2 to 60, preferably from 2 to 40, still more preferably from 2 to 20.
在本發明中，環烷基包含具有3至60個碳原子之單環或多環，且可額外經由另一取代基所取代。於此，多環表示環烷基直接連結至或融合至另一環基。於此，另一環基亦可為環烷基，但也可為其他種環基，例如：雜環烷基、芳基、雜芳基等。環烷基的碳原子數可為3至60，較佳為3至40、再更佳為5至20。具體的範例包含環丙基、環丁基、環戊基、3-甲基環戊基、2,3-二甲基環戊基、環己基、3-甲基環己基、4-甲基環己基、2,3-二甲基環己基、3,4,5-三甲基環己基、4-叔丁基環己基、環庚基、環辛基等，但本發明不限於此。In the present invention, a cycloalkyl group includes a monocyclic or polycyclic ring having 3 to 60 carbon atoms, and may be additionally substituted with another substituent. Herein, the polycyclic ring means that the cycloalkyl group is directly bonded to or fused to another ring group. Here, the other cyclic group may also be a cycloalkyl group, but may be other kinds of cyclic groups such as a heterocycloalkyl group, an aryl group, a heteroaryl group and the like. The cycloalkyl group may have a carbon number of from 3 to 60, preferably from 3 to 40, still more preferably from 5 to 20. Specific examples include cyclopropyl, cyclobutyl, cyclopentyl, 3-methylcyclopentyl, 2,3-dimethylcyclopentyl, cyclohexyl, 3-methylcyclohexyl, 4-methylcyclo Hexyl, 2,3-dimethylcyclohexyl, 3,4,5-trimethylcyclohexyl, 4-tert-butylcyclohexyl, cycloheptyl, cyclooctyl or the like, but the invention is not limited thereto.
在本發明中，雜環烷基包含氧(O)、硫(S)、硒(Se)、氮(N)、或矽(Si)作為雜原子，包含具有2至60個碳原子之單環或多環，且可額外經由另一取代基所取代。於此，多環表示雜環烷基直接連結至或融合至另一環基。於此，另一環基亦可為雜環烷基，但也可為其他種環基，例如：環烷基、芳基、雜芳基等。雜環烷基的碳原子數可為2至60，較佳為2至40、再更佳為3至20。In the present invention, a heterocycloalkyl group includes oxygen (O), sulfur (S), selenium (Se), nitrogen (N), or cerium (Si) as a hetero atom, and includes a single ring having 2 to 60 carbon atoms. Or polycyclic, and may be additionally substituted with another substituent. Herein, the polycyclic ring means that the heterocycloalkyl group is directly bonded to or fused to another ring group. Here, the other cyclic group may be a heterocycloalkyl group, but may be other kinds of cyclic groups such as a cycloalkyl group, an aryl group, a heteroaryl group and the like. The heterocycloalkyl group may have 2 to 60 carbon atoms, preferably 2 to 40, still more preferably 3 to 20 carbon atoms.
在本發明中，芳基包含具有6至60個碳原子之單環或多環，且可額外經由另一取代基所取代。於此，多環表示芳基直接連結至或融合至另一環基。於此，另一環基亦可為芳基，但也可為其他種環基，例如：環烷基、雜環烷基、雜芳基等。芳基包含螺環基(spiro group)。芳基的碳原子數可為6至60，較佳為6至40、再更佳為6至25。芳基的具體範例包含：苯基、聯苯基、三苯基、萘基、蒽基、䓛基(chrysenyl group)、菲基、苝基、熒蒽基、三亞苯基、萉基(phenalenyl group)、芘基、並四苯基(tetracenyl group)、並五苯基(pentacenyl group)、芴基、茚基、苊基、苯並芴基(benzofluorenyl group)、螺二芴基(spirobifluorenyl group)、2,3-二氫-1H-茚基、其融合環基等，但本發明不限於此。In the present invention, the aryl group contains a monocyclic or polycyclic ring having 6 to 60 carbon atoms, and may be additionally substituted with another substituent. Herein, the polycyclic ring means that the aryl group is directly bonded to or fused to another ring group. Here, the other cyclic group may also be an aryl group, but may be other kinds of cyclic groups such as a cycloalkyl group, a heterocycloalkyl group, a heteroaryl group and the like. The aryl group contains a spiro group. The aryl group may have a carbon number of from 6 to 60, preferably from 6 to 40, still more preferably from 6 to 25. Specific examples of the aryl group include: phenyl, biphenyl, triphenyl, naphthyl, anthracenyl, chrysenyl group, phenanthryl, anthracenyl, fluoranthene, triphenylene, phenalenyl group , fluorenyl, tetracenyl group, pentacenyl group, sulfhydryl, fluorenyl, fluorenyl, benzofluorenyl group, spirobifluorenyl group, 2,3-Dihydro-1H-indenyl, a fused ring group or the like, but the invention is not limited thereto.
在本發明中，螺環基為包含螺結構的基團，且可具有15至60個碳原子。例如，螺環基可包含2,3-二氫-1H-茚基或環己烷基以螺旋式鍵結至芴基之結構。具體而言，螺環基可包含下列結構式中的任一個基團：、、、、、、。In the present invention, the spiro group is a group containing a spiro structure and may have 15 to 60 carbon atoms. For example, a spiro group may comprise a structure in which a 2,3-dihydro-1H-indenyl group or a cyclohexane group is helically bonded to a fluorenyl group. In particular, the spiro group may comprise any of the following structural formulas: , , , , , , .
在本發明中，雜芳基包含氧(O)、硫(S)、硒(Se)、氮(N)、或矽(Si)作為雜原子，包含具有2至60個碳原子之單環或多環，且可額外經由另一取代基所取代。於此，多環表示雜芳基直接連結至或融合至另一環基。於此，另一環基亦可為雜芳基，但也可為其他種環基，例如：環烷基、雜環烷基、芳基等。雜芳基的碳原子數可為2至60，較佳為2至40、再更佳為3至25。雜芳基的具體範例包含：吡啶基、吡咯基、嘧啶基、噠嗪基、呋喃基、噻吩基、咪唑基、吡唑基、噁唑基、異噁唑基、噻唑基、異噻唑基、***基、呋吖基(furazanyl group) 、惡二唑基、噻二唑基(thiadiazolyl group)、二噻唑基(dithiazolyl group) 、四唑基、吡喃基、噻喃基、二嗪基、惡嗪基、噻嗪基、二氧雜環己基(dioxinyl group) 、三嗪基、四嗪基、喹啉基、異喹啉基、喹唑啉基(quinazolinyl group)、異喹唑啉基、喹唑啉基(quinozolilyl group)、氮雜萘基 (naphthyridyl group)、吖啶基、菲啶基(phenanthridinyl group)、咪唑並吡啶基、二氮亞萘基(diaza naphthalenyl group)、三氮茚基(triazaindene group)、吲哚基、吲哚嗪基(indolizinyl group)、苯並噻唑基、苯並噁唑基、苯並咪唑基、苯並噻吩基、苯並呋喃基、二苯並噻吩基、二苯並呋喃基、咔唑基、苯並咔唑基、二苯並咔唑基、吩嗪基、二苯並噻咯基、螺二（二苯並噻咯）、二氫吩嗪基、吩惡嗪基(phenoxazinyl group)，菲啶基(phenanthridyl group)、咪唑並吡啶基、噻吩基、吲哚並[2,3-a]咔唑基、吲哚並[2,3-b]咔唑基、吲哚啉基、10,11-二氫二苯並[b, f] 氮呯基(10,11-dihydro-dibenzo[b,f]azepin group)、9,10- 二氫吖啶基、菲三嗪基(phenanthrazinyl group)、吩噻嗪基、酞嗪基、萘啶基(naphthylidinyl group)、菲咯啉基(phenanthrolinyl group)、苯並[c] [1,2,5]噻二唑基、5,10-二氫二苯並[b, e] [1,4] azasilinyl、吡唑並[1,5-C]喹唑啉基、吡啶並[1,2-b ]吲唑基、吡啶並[1,2-a]咪唑並[1,2-e]二氫吲哚基、5,11-二氫茚並[1,2-b]咔唑基等，但本發明不限於此。In the present invention, the heteroaryl group includes oxygen (O), sulfur (S), selenium (Se), nitrogen (N), or cerium (Si) as a hetero atom, and includes a single ring having 2 to 60 carbon atoms or Polycyclic, and may be additionally substituted with another substituent. Herein, polycyclic means that the heteroaryl group is directly bonded to or fused to another ring group. Here, the other cyclic group may be a heteroaryl group, but may be other kinds of cyclic groups such as a cycloalkyl group, a heterocycloalkyl group, an aryl group and the like. The heteroaryl group may have a carbon number of 2 to 60, preferably 2 to 40, still more preferably 3 to 25. Specific examples of heteroaryl groups include: pyridyl, pyrrolyl, pyrimidinyl, pyridazinyl, furyl, thienyl, imidazolyl, pyrazolyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, Triazolyl, furazanyl group, oxadiazolyl, thiadiazolyl group, dithiazolyl group, tetrazolyl, pyranyl, thiopyranyl, diazinyl, Oxazinyl, thiazinyl, dioxinyl group, triazinyl, tetrazinyl, quinolyl, isoquinolinyl, quinazolinyl group, isoquinazolinyl, Quinozolilyl group, naphthyridyl group, acridinyl group, phenanthridinyl group, imidazopyridyl group, diaza naphthalenyl group, triazinyl group (triazaindene group), anthracenyl, indolizinyl group, benzothiazolyl, benzoxazolyl, benzimidazolyl, benzothienyl, benzofuranyl, dibenzothiophenyl, Dibenzofuranyl, oxazolyl, benzoxazolyl, dibenzoxazolyl, phenazinyl, dibenzothiol , spirobi (dibenzothiazole), dihydrophenazinyl, phenoxazinyl group, phenanthridyl group, imidazopyridyl, thienyl, anthracene [2,3- a] carbazolyl, indolo[2,3-b]oxazolyl, porphyrinyl, 10,11-dihydrodibenzo[b,f]azinyl (10,11-dihydro-dibenzo [b,f]azepin group), 9,10-dihydroacridinyl, phenanthrazinyl group, phenothiazine group, pyridazinyl, naphthylidinyl group, phenanthroline group Phenanthrolinyl group), benzo[c][1,2,5]thiadiazolyl, 5,10-dihydrodibenzo[b,e][1,4] azasilinyl, pyrazolo[1,5- C] quinazolinyl, pyrido[1,2-b]carbazolyl, pyrido[1,2-a]imidazo[1,2-e]indanyl, 5, 11-Dihydroindeno[1,2-b]carbazolyl or the like, but the invention is not limited thereto.
在本發明中，胺基可選自由：單烷胺基；單芳胺基；單雜芳胺基；-NH2；二烷胺基；二芳胺基；二雜芳胺基；烷芳胺基；烷雜芳胺基；及芳雜芳胺基所組成之群組，且其之碳原子數並無特別限制，但較佳可為1至30個。胺基的具體範例包含：甲胺基、二甲胺基、乙胺基、二乙胺基、苯胺基、萘胺基、聯苯胺基、二聯苯胺基、蒽胺基、9-甲基-蒽胺基、二苯胺基、苯萘胺基、二甲苯胺基(ditolylamine group)、苯基甲苯胺基、三聯苯胺基、聯苯萘胺基、苯基聯苯胺基、聯苯基芴胺基、苯基三聯苯烯胺基(phenyltriphenylenylamine group)、聯苯基三聯苯烯胺基(biphenyltriphenylenylamine group)等，但本發明不限於此。In the present invention, the amine group may be selected from the group consisting of monoalkylamino groups; monoarylamine groups; monoheteroarylamino groups; -NH2; dialkylamino groups; diarylamine groups; diheteroarylamino groups; alkylarylamine groups. The group consisting of an alkanoarylamine group and an aromatic heteroarylamino group, and the number of carbon atoms thereof is not particularly limited, but may preferably be from 1 to 30. Specific examples of the amine group include: methylamino group, dimethylamino group, ethylamino group, diethylamino group, anilino group, naphthylamino group, benzidine group, diphenylanilide group, decylamino group, 9-methyl group- Amidino, diphenylamino, phenylnaphthylamine, ditolylamine group, phenyltoluylamine, terphenylamine, biphenylnaphthylamine, phenylbenzidine, biphenylguanidino And a phenyltriphenylenylamine group, a biphenyltriphenylenylamine group, or the like, but the invention is not limited thereto.
在本發明中，亞芳基表示芳基中有兩個鍵結位置，即二價基團。除了這些亞芳基各自為二價基團以外，上述對芳基的描述亦可應用於此。此外，雜亞芳基表示雜芳基中有兩個鍵結位置，即二價基團。除了這些雜亞芳基各自為二價基團以外，上述對雜芳基的描述亦可應用於此。In the present invention, an arylene group means that there are two bonding sites in the aryl group, that is, a divalent group. In addition to the fact that these arylene groups are each a divalent group, the above description of the aryl group can also be applied thereto. Further, a heteroarylene group means that there are two bonding sites in the heteroaryl group, that is, a divalent group. In addition to the fact that these heteroarylene groups are each a divalent group, the above description of the heteroaryl group can also be applied thereto.
根據本發明一實施例，式1可由下式2所示： [式2]於式2中，R1至R8係與式1中定義相同。According to an embodiment of the present invention, Equation 1 can be expressed by the following Equation 2: [Formula 2] In Formula 2, R1 to R8 are the same as defined in Formula 1.
此外，根據本發明一實施例，式1可由下式3所示： [式3]於式3中，R1至R8係與式1中定義相同。Further, according to an embodiment of the present invention, Equation 1 can be expressed by the following Equation 3: [Formula 3] In Formula 3, R1 to R8 are the same as defined in Formula 1.
根據本發明一實施例，R1和R2中至少一個為經取代或未經取代之單環或多環C6 至C60 芳基；經取代或未經取代之單環或多環C2 至C60 雜芳基；-SiRR’R”； -P(=O)RR’；或–NRR’；以及R、R’、及R” 係互相相同或不同，且各自獨立選自由：氫；氘；經取代或未經取代之直鏈或支鏈C1 至C60 烷基；經取代或未經取代之單環或多環C3 至C60 環烷基；經取代或未經取代之單環或多環C6 至C60 芳基；及經取代或未經取代之單環或多環C2 至C60 雜芳基所組成之群組。According to an embodiment of the invention, at least one of R1 and R2 is a substituted or unsubstituted monocyclic or polycyclic C 6 to C 60 aryl; substituted or unsubstituted monocyclic or polycyclic C 2 to C 60 heteroaryl; -SiRR'R "; -P (= O ) RR '; or -NRR'; and R, R ', and R" are the same or different from each other based, and are each independently selected from the group consisting of: hydrogen; deuterium; Substituted or unsubstituted linear or branched C 1 to C 60 alkyl; substituted or unsubstituted monocyclic or polycyclic C 3 to C 60 cycloalkyl; substituted or unsubstituted monocyclic ring Or a polycyclic C 6 to C 60 aryl group; and a group of substituted or unsubstituted monocyclic or polycyclic C 2 to C 60 heteroaryl groups.
根據本發明一實施例，R1為經取代或未經取代之單環或多環C6 至C60 芳基；經取代或未經取代之單環或多環C2 至C60 雜芳基；-SiRR’R”； -P(=O)RR’；或–NRR’；以及R、R’、及R”係與上述相同，且R2為氫；氘；或經取代或未經取代之單環或多環C6 至C60 芳基。According to an embodiment of the invention, R1 is a substituted or unsubstituted monocyclic or polycyclic C 6 to C 60 aryl; substituted or unsubstituted monocyclic or polycyclic C 2 to C 60 heteroaryl; -SiRR'R";-P(=O)RR'; or -NRR'; and R, R', and R" are the same as above, and R2 is hydrogen; hydrazine; or substituted or unsubstituted single Ring or polycyclic C 6 to C 60 aryl.
根據本發明一實施例，R2為經取代或未經取代之單環或多環C6 至C60 芳基；經取代或未經取代之單環或多環C2 至C60 雜芳基；-SiRR’R”； -P(=O)RR’；或–NRR’；以及R、R’、及R”係與上述相同，且R1為氫；氘；或經取代或未經取代之單環或多環C6 至C60 芳基。According to an embodiment of the invention, R 2 is a substituted or unsubstituted monocyclic or polycyclic C 6 to C 60 aryl; substituted or unsubstituted monocyclic or polycyclic C 2 to C 60 heteroaryl; -SiRR'R";-P(=O)RR'; or -NRR'; and R, R', and R" are the same as above, and R1 is hydrogen; hydrazine; or substituted or unsubstituted single Ring or polycyclic C 6 to C 60 aryl.
根據本發明一實施例，R、R’、及R” 係互相相同或不同，且各自獨立為經取代或未經取代之單環或多環C6 至C60 芳基；或經取代或未經取代之單環或多環C2 至C60 雜芳基。According to an embodiment of the invention, R, R', and R" are the same or different from each other, and are each independently substituted or unsubstituted monocyclic or polycyclic C 6 to C 60 aryl; or substituted or not Monocyclic or polycyclic C 2 to C 60 heteroaryl groups substituted.
根據本發明一實施例，R、R’、及R” 係互相相同或不同，且各自獨立選自由：苯基、聯苯基、萘基、吡啶基、嘧啶基、蒽基、菲基、䓛基、三亞苯基、芘基、芴基、二甲基芴基、咔唑基、二苯並呋喃基和二苯並噻吩所組成之群組。According to an embodiment of the invention, R, R', and R" are the same or different from each other, and are each independently selected from the group consisting of: phenyl, biphenyl, naphthyl, pyridyl, pyrimidinyl, fluorenyl, phenanthryl, anthracene a group consisting of a benzyl group, a triphenylene group, a fluorenyl group, a fluorenyl group, a dimethyl fluorenyl group, a carbazolyl group, a dibenzofuranyl group, and a dibenzothiophene group.
根據本發明一實施例，在式1中，R3至R8為氫；氘；或經取代或未經取代之單環或多環C6 至C30 芳基。According to an embodiment of the present invention, in Formula 1, R3 to R8 are hydrogen; hydrazine; or a substituted or unsubstituted monocyclic or polycyclic C 6 to C 30 aryl group.
根據本發明一實施例，R3至R8為氫或氘。According to an embodiment of the invention, R3 to R8 are hydrogen or helium.
根據本發明一實施例，在式1中，R1及R2中至少一個為-(L)m-(Z)n； L為一直接鍵結；經取代或未經取代之單環或多環C6 至C60 亞芳基；或經取代或未經取代之單環或多環C2 至C60 雜亞芳基； m為0至3之整數； n為1至5之整數； Z係選自由：經取代或未經取代之單環或多環C6 至C60 芳基；經取代或未經取代之單環或多環C2 至C60 雜芳基；-SiRR’R”； -P(=O)RR’；及–NRR’所組成之群組；以及 R、R’、及R” 係互相相同或不同，且各自獨立選自由：氫；氘；經取代或未經取代之直鏈或支鏈C1 至C60 烷基；經取代或未經取代之單環或多環C3 至C60 環烷基；經取代或未經取代之單環或多環C6 至C60 芳基；及經取代或未經取代之單環或多環C2 至C60 雜芳基所組成之群組。According to an embodiment of the present invention, in Formula 1, at least one of R1 and R2 is -(L)m-(Z)n; L is a direct bond; a substituted or unsubstituted monocyclic or polycyclic C 6 to C 60 arylene; or substituted or unsubstituted monocyclic or polycyclic C 2 to C 60 heteroarylene; m is an integer from 0 to 3; n is an integer from 1 to 5; Free: substituted or unsubstituted monocyclic or polycyclic C 6 to C 60 aryl; substituted or unsubstituted monocyclic or polycyclic C 2 to C 60 heteroaryl; -SiRR'R"; a group of P(=O)RR'; and -NRR'; and R, R', and R" are the same or different from each other, and are each independently selected from: hydrogen; hydrazine; substituted or unsubstituted Linear or branched C 1 to C 60 alkyl; substituted or unsubstituted monocyclic or polycyclic C 3 to C 60 cycloalkyl; substituted or unsubstituted monocyclic or polycyclic C 6 to C a group consisting of a 60 aryl group; and a substituted or unsubstituted monocyclic or polycyclic C 2 to C 60 heteroaryl group.
根據本發明一實施例，L為一直接鍵結；經取代或未經取代之C6 至C20 亞芳基；或經取代或未經取代之含氮C2 至C20 雜亞芳基。According to an embodiment of the invention, L is a direct bond; a substituted or unsubstituted C 6 to C 20 arylene; or a substituted or unsubstituted nitrogen-containing C 2 to C 20 heteroarylene.
根據本發明一實施例，L為一直接鍵結； C6 至C20 亞芳基；或含氮C2 至C20 雜亞芳基。According to an embodiment of the invention, L is a direct bond; a C 6 to C 20 arylene group; or a nitrogen-containing C 2 to C 20 heteroarylene group.
根據本發明一實施例，L為一直接鍵結；或亞苯基；亞萘基；亞蒽基；亞吡啶基；亞嘧啶基；或亞三嗪基，且可進一步被氟(F)取代。According to an embodiment of the present invention, L is a direct bond; or a phenylene group; a naphthylene group; an anthranylene group; a pyridylene group; a pyrimidylene group; or a tritriazinyl group, and may be further substituted by fluorine (F) .
根據本發明一實施例，R、R’、及R” 係互相相同或不同，且各自獨立為經取代或未經取代之單環或多環C6 至C60 芳基；或經取代或未經取代之單環或多環C2 至C60 雜芳基。According to an embodiment of the invention, R, R', and R" are the same or different from each other, and are each independently substituted or unsubstituted monocyclic or polycyclic C 6 to C 60 aryl; or substituted or not Monocyclic or polycyclic C 2 to C 60 heteroaryl groups substituted.
根據本發明一實施例，R、R’、及R” 係互相相同或不同，且各自獨立選自由：苯基、聯苯基、萘基、吡啶基、嘧啶基、蒽基、菲基、䓛基、三亞苯基、芘基、芴基、二甲基芴基、咔唑基、二苯並呋喃基和二苯並噻吩所組成之群組。According to an embodiment of the invention, R, R', and R" are the same or different from each other, and are each independently selected from the group consisting of: phenyl, biphenyl, naphthyl, pyridyl, pyrimidinyl, fluorenyl, phenanthryl, anthracene a group consisting of a benzyl group, a triphenylene group, a fluorenyl group, a fluorenyl group, a dimethyl fluorenyl group, a carbazolyl group, a dibenzofuranyl group, and a dibenzothiophene group.
根據本發明一實施例，Z為經取代或未經取代之單環或多環C6 至C60 芳基。According to an embodiment of the invention, Z is a substituted or unsubstituted monocyclic or polycyclic C 6 to C 60 aryl group.
根據本發明一實施例，Z為經取代或未經取代之苯基、經取代或未經取代之聯苯基、經取代或未經取代之萘基、經取代或未經取代之䓛基、經取代或未經取代之芘基、經取代或未經取代之三亞苯基、經取代或未經取代之蒽基、經取代或未經取代之菲基、經取代或未經取代之芴基、或經取代或未經取代之螺二芴基。According to an embodiment of the invention, Z is substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted fluorenyl, Substituted or unsubstituted fluorenyl, substituted or unsubstituted triphenylene, substituted or unsubstituted fluorenyl, substituted or unsubstituted phenanthryl, substituted or unsubstituted fluorenyl Or a substituted or unsubstituted spirobifluorenyl group.
根據本發明一實施例，Z為經取代或未經取代之苯基、經取代或未經取代之聯苯基、經取代或未經取代之萘基、經取代或未經取代之䓛基、經取代或未經取代之芘基、經取代或未經取代之三亞苯基、經取代或未經取代之蒽基、經取代或未經取代之菲基、經取代或未經取代之芴基、或經取代或未經取代之螺二芴基；「經取代或未經取代」一詞表示未經取代或經下述至少一個所取代：鹵素、-CN、直鏈或支鏈C1 至C60 烷基、經取代或未經取代之單環或多環C3 至C60 環烷基、單環或多環C6 至C60 芳基、及單環或多環C2 至C60 雜芳基，且該些基團可再進一步被取代。According to an embodiment of the invention, Z is substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted fluorenyl, Substituted or unsubstituted fluorenyl, substituted or unsubstituted triphenylene, substituted or unsubstituted fluorenyl, substituted or unsubstituted phenanthryl, substituted or unsubstituted fluorenyl or a substituted or unsubstituted spirobifluorene group of; "substituted or unsubstituted" term represents an unsubstituted or substituted by at least one of the following: halogen, -CN, a straight or branched chain C 1 to C 60 alkyl, substituted or unsubstituted monocyclic or polycyclic C 3 to C 60 cycloalkyl, monocyclic or polycyclic C 6 to C 60 aryl, and monocyclic or polycyclic C 2 to C 60 Heteroaryl groups, and these groups can be further substituted.
根據本發明一實施例，Z為經取代或未經取代之苯基、經取代或未經取代之聯苯基、經取代或未經取代之萘基、經取代或未經取代之䓛基、經取代或未經取代之芘基、經取代或未經取代之三亞苯基、經取代或未經取代之蒽基、經取代或未經取代之菲基、經取代或未經取代之芴基、或經取代或未經取代之螺二芴基；「經取代或未經取代」一詞表示未經取代或經下述至少一個所取代：鹵素、-CN、甲基、環己基、苯基、聯苯基、萘基、吡啶基、及咔唑基，且該些基團可再進一步被取代。According to an embodiment of the invention, Z is substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted fluorenyl, Substituted or unsubstituted fluorenyl, substituted or unsubstituted triphenylene, substituted or unsubstituted fluorenyl, substituted or unsubstituted phenanthryl, substituted or unsubstituted fluorenyl Or substituted or unsubstituted spirobiindole; the term "substituted or unsubstituted" means unsubstituted or substituted by at least one of: halogen, -CN, methyl, cyclohexyl, phenyl And a biphenyl group, a naphthyl group, a pyridyl group, and a carbazolyl group, and the groups may be further substituted.
根據本發明一實施例，Z為經取代或未經取代之單環或多環C2 至C60 雜芳基；且該雜芳基包含氮(N) 、氧(O)、硫(S)、矽(Si) 、或硒(Se)作為雜原子。According to an embodiment of the invention, Z is a substituted or unsubstituted monocyclic or polycyclic C 2 to C 60 heteroaryl; and the heteroaryl comprises nitrogen (N), oxygen (O), sulfur (S) , 矽 (Si), or selenium (Se) as a hetero atom.
根據本發明一實施例，Z為經取代或未經取代之苯並咪唑基、經取代或未經取代之喹啉基、經取代或未經取代之異喹啉基、經取代或未經取代之萘啶基、經取代或未經取代之喹唑啉基(quinazolinyl group)、經取代或未經取代之喹喔啉基(quinoxalinyl group)、經取代或未經取代之噌嗪基(cinolinyl group)、經取代或未經取代之苯並噻唑基、經取代或未經取代之苯並噁唑基、經取代或未經取代之噁二唑基、經取代或未經取代之二苯並呋喃基、經取代或未經取代之二苯並噻吩基、經取代或未經取代之吡啶基、經取代或未經取代之嘧啶基、經取代或未經取代之三嗪基、經取代或未經取代之吡唑並酞嗪基(pyrazolophthalazinyl group)、經取代或未經取代之吡唑並喹唑啉基(pyrazoloquinazolinyl group)、經取代或未經取代之吡啶並吲唑基(pyridoindazolyl group)、或經取代或未經取代之咔唑基。According to an embodiment of the invention, Z is substituted or unsubstituted benzimidazolyl, substituted or unsubstituted quinolinyl, substituted or unsubstituted isoquinolyl, substituted or unsubstituted Naphthyridinyl, substituted or unsubstituted quinazolinyl group, substituted or unsubstituted quinoxalinyl group, substituted or unsubstituted cinolinyl group , substituted or unsubstituted benzothiazolyl, substituted or unsubstituted benzoxazolyl, substituted or unsubstituted oxadiazolyl, substituted or unsubstituted dibenzofuran a substituted or unsubstituted dibenzothiophenyl group, a substituted or unsubstituted pyridyl group, a substituted or unsubstituted pyrimidinyl group, a substituted or unsubstituted triazinyl group, substituted or unsubstituted a substituted pyrazolophthalazinyl group, a substituted or unsubstituted pyrazoloquinazolinyl group, a substituted or unsubstituted pyridodoindazolyl group, Or substituted or unsubstituted carbazolyl.
根據本發明一實施例，Z為經取代或未經取代之苯並咪唑基、經取代或未經取代之喹啉基、經取代或未經取代之異喹啉基、經取代或未經取代之萘啶基、經取代或未經取代之喹唑啉基(quinazolinyl group)、經取代或未經取代之喹喔啉基(quinoxalinyl group)、經取代或未經取代之噌嗪基(cinolinyl group)、經取代或未經取代之苯並噻唑基、經取代或未經取代之苯並噁唑基、經取代或未經取代之噁二唑基、經取代或未經取代之二苯並呋喃基、經取代或未經取代之二苯並噻吩基、經取代或未經取代之吡啶基、經取代或未經取代之嘧啶基、經取代或未經取代之三嗪基、經取代或未經取代之吡唑並酞嗪基(pyrazolophthalazinyl group)、經取代或未經取代之吡唑並喹唑啉基(pyrazoloquinazolinyl group)、經取代或未經取代之吡啶並吲唑基(pyridoindazolyl group)、或經取代或未經取代之咔唑基；「經取代或未經取代」一詞表示未經取代或經下述至少一個所取代：鹵素、-CN、單環或多環C3 至C60 環烷基、單環或多環C6 至C60 芳基、及單環或多環C2 至C60 雜芳基，且該些基團可再進一步被取代。According to an embodiment of the invention, Z is substituted or unsubstituted benzimidazolyl, substituted or unsubstituted quinolinyl, substituted or unsubstituted isoquinolyl, substituted or unsubstituted Naphthyridinyl, substituted or unsubstituted quinazolinyl group, substituted or unsubstituted quinoxalinyl group, substituted or unsubstituted cinolinyl group , substituted or unsubstituted benzothiazolyl, substituted or unsubstituted benzoxazolyl, substituted or unsubstituted oxadiazolyl, substituted or unsubstituted dibenzofuran a substituted or unsubstituted dibenzothiophenyl group, a substituted or unsubstituted pyridyl group, a substituted or unsubstituted pyrimidinyl group, a substituted or unsubstituted triazinyl group, substituted or unsubstituted a substituted pyrazolophthalazinyl group, a substituted or unsubstituted pyrazoloquinazolinyl group, a substituted or unsubstituted pyridodoindazolyl group, Or substituted or unsubstituted carbazolyl; A substituted or unsubstituted term "means unsubstituted or substituted by at least one of the following: halogen, -CN, monocyclic or polycyclic C 3 to C 60 cycloalkyl, monocyclic or polycyclic C 6 to C 60 Aryl, and monocyclic or polycyclic C 2 to C 60 heteroaryl groups, and these groups may be further substituted.
根據本發明一實施例，Z為經取代或未經取代之苯並咪唑基、經取代或未經取代之喹啉基、經取代或未經取代之異喹啉基、經取代或未經取代之萘啶基、經取代或未經取代之喹唑啉基(quinazolinyl group)、經取代或未經取代之喹喔啉基(quinoxalinyl group)、經取代或未經取代之噌嗪基(cinolinyl group)、經取代或未經取代之苯並噻唑基、經取代或未經取代之苯並噁唑基、經取代或未經取代之噁二唑基、經取代或未經取代之二苯並呋喃基、經取代或未經取代之二苯並噻吩基、經取代或未經取代之吡啶基、經取代或未經取代之嘧啶基、經取代或未經取代之三嗪基、經取代或未經取代之吡唑並酞嗪基(pyrazolophthalazinyl group)、經取代或未經取代之吡唑並喹唑啉基(pyrazoloquinazolinyl group)、經取代或未經取代之吡啶並吲唑基(pyridoindazolyl group)、或經取代或未經取代之咔唑基；「經取代或未經取代」一詞表示未經取代或經下述至少一個所取代：鹵素、-CN、環己基、苯基、萘基、及吡啶基，且該些基團可再進一步被取代。According to an embodiment of the invention, Z is substituted or unsubstituted benzimidazolyl, substituted or unsubstituted quinolinyl, substituted or unsubstituted isoquinolyl, substituted or unsubstituted Naphthyridinyl, substituted or unsubstituted quinazolinyl group, substituted or unsubstituted quinoxalinyl group, substituted or unsubstituted cinolinyl group , substituted or unsubstituted benzothiazolyl, substituted or unsubstituted benzoxazolyl, substituted or unsubstituted oxadiazolyl, substituted or unsubstituted dibenzofuran a substituted or unsubstituted dibenzothiophenyl group, a substituted or unsubstituted pyridyl group, a substituted or unsubstituted pyrimidinyl group, a substituted or unsubstituted triazinyl group, substituted or unsubstituted a substituted pyrazolophthalazinyl group, a substituted or unsubstituted pyrazoloquinazolinyl group, a substituted or unsubstituted pyridodoindazolyl group, Or substituted or unsubstituted carbazolyl; Halogen, -CN, a cyclohexyl group, a phenyl group, a naphthyl group, and pyridyl group, and the plurality of groups may be further substituted: The word "represents an unsubstituted or substituted by at least one of the following generations or unsubstituted.
根據本發明一實施例，Z為，以及X1及X2係互相相同或不同，且各自獨立為經取代或未經取代之單環或多環C6 至C60 芳香烴環；或經取代或未經取代之單環或多環C2 至C60 芳香雜環。According to an embodiment of the invention, Z is And X1 and X2 are the same or different from each other, and each independently is a substituted or unsubstituted monocyclic or polycyclic C 6 to C 60 aromatic hydrocarbon ring; or a substituted or unsubstituted monocyclic or polycyclic C 2 to C 60 aromatic heterocyclic ring.
根據本發明一實施例，其中係由下列結構式中任一個所示：、、、、、。According to an embodiment of the invention, wherein It is shown by any of the following structural formulas: , , , , , .
在該些結構式中，Z1 至Z3 係為互相相同或不同，且各自獨立為S或O；Z4 至Z9 係為互相相同或不同，且各自獨立為CY’Y”、NY’、S、或O；以及Y’及Y” 係為互相相同或不同，且各自獨立為氫；氘；經取代或未經取代之直鏈或支鏈C1 至C60 烷基；或經取代或未經取代之單環或多環C6 至C60 芳基。In the structural formulas, Z 1 to Z 3 are the same or different from each other, and each is independently S or O; Z 4 to Z 9 are the same or different from each other, and each is independently CY'Y", NY' , S, or O; and Y' and Y" are the same or different from each other and are each independently hydrogen; hydrazine; substituted or unsubstituted linear or branched C 1 to C 60 alkyl; or substituted Or unsubstituted monocyclic or polycyclic C 6 to C 60 aryl.
根據本發明一實施例，Y’及Y”係為互相相同或不同，且各自獨立為氫；氘；甲基；苯基；或萘基。According to an embodiment of the invention, Y' and Y" are the same or different from each other and are each independently hydrogen; hydrazine; methyl; phenyl; or naphthyl.
根據本發明一實施例，Z為-SiRR’R”，且R、R’、及R” 係互相相同或不同，且各自獨立選自由：經取代或未經取代之直鏈或支鏈C1 至C60 烷基；經取代或未經取代之單環或多環C6 至C60 芳基；及經取代或未經取代之單環或多環C2 至C60 雜芳基所組成之群組。According to an embodiment of the invention, Z is -SiRR'R", and R, R', and R" are the same or different from each other, and are each independently selected from: a substituted or unsubstituted linear or branched C 1 a C 60 alkyl group; a substituted or unsubstituted monocyclic or polycyclic C 6 to C 60 aryl group; and a substituted or unsubstituted monocyclic or polycyclic C 2 to C 60 heteroaryl group; Group.
根據本發明一實施例，Z為-SiRR’R” ，且R、R’、及R” 係互相相同或不同，且為單環或多環C6 至C60 芳基。According to an embodiment of the invention, Z is -SiRR'R", and R, R', and R" are the same or different from each other, and are monocyclic or polycyclic C 6 to C 60 aryl.
根據本發明一實施例，Z為-SiRR’R” ，且R、R’、及R” 係互相相同或不同，且為苯基或聯苯基。According to an embodiment of the invention, Z is -SiRR'R" and R, R', and R" are the same or different from each other and are phenyl or biphenyl.
根據本發明一實施例，Z為-P(=O)RR’ ，且R和R’ 係互相相同或不同，且各自獨立選自由：經取代或未經取代之直鏈或支鏈C1 至C60 烷基；經取代或未經取代之單環或多環C6 至C60 芳基；及經取代或未經取代之單環或多環C2 至C60 雜芳基所組成之群組。According to an embodiment of the present invention, Z is -P (= O) RR ', and R and R' are the same or different from each other based, and are each independently selected from the group consisting of: substituted or non-substituted straight chain or branched chain C 1 to a C 60 alkyl group; a substituted or unsubstituted monocyclic or polycyclic C 6 to C 60 aryl group; and a substituted or unsubstituted monocyclic or polycyclic C 2 to C 60 heteroaryl group group.
根據本發明一實施例，Z為-P(=O)RR’ ，且R和R’ 係互相相同或不同，且為單環或多環C6 至C60 芳基。According to an embodiment of the present invention, Z is -P (= O) RR ', and R and R' are the same or different from each other train and is a monocyclic or polycyclic C 6 to C 60 aryl group.
根據本發明一實施例，Z為-P(=O)RR’，且R和R’ 係互相相同或不同，且為苯基或聯苯基。According to an embodiment of the invention, Z is -P(=O)RR', and R and R' are the same or different from each other and are phenyl or biphenyl.
根據本發明一實施例，Z為–NRR’，且R和R’ 係互相相同或不同，且各自獨立選自由：經取代或未經取代之直鏈或支鏈C1 至C60 烷基；經取代或未經取代之單環或多環C6 至C60 芳基；及經取代或未經取代之單環或多環C2 至C60 雜芳基所組成之群組。According to an embodiment of the invention, Z is -NRR', and R and R' are the same or different from each other, and are each independently selected from: a substituted or unsubstituted linear or branched C 1 to C 60 alkyl group; a substituted or unsubstituted monocyclic or polycyclic C 6 to C 60 aryl group; and a substituted or unsubstituted monocyclic or polycyclic C 2 to C 60 heteroaryl group.
根據本發明一實施例，Z為–NRR’，且R和R’ 係互相相同或不同，且為單環或多環C6 至C60 芳基；或經取代或未經取代之單環或多環C2 至C60 雜芳基。According to an embodiment of the invention, Z is -NRR', and R and R' are the same or different from each other, and are monocyclic or polycyclic C 6 to C 60 aryl; or substituted or unsubstituted monocyclic or Polycyclic C 2 to C 60 heteroaryl.
根據本發明一實施例，Z為–NRR’，且R和R’可選自由：苯基、聯苯基、萘基、芴基、二甲基芴基、二苯並呋喃基、二苯並噻吩基和咔唑基所組成之群組。According to an embodiment of the invention, Z is -NRR', and R and R' are optionally free of: phenyl, biphenyl, naphthyl, anthracenyl, dimethylindenyl, dibenzofuranyl, dibenzo A group consisting of a thienyl group and a carbazolyl group.
式1之化合物可包含兩個以上核心結構。The compound of Formula 1 may contain more than two core structures.
根據本發明一實施例，式1係由下列式4或式5所示： [式4][式 5]於式4及式5中， A及A’係各自獨立選自由：一直接鍵結；經取代或未經取代之直鏈或支鏈C2 至C60 亞烷基；經取代或未經取代之直鏈或支鏈C2 至C60 亞烯基；經取代或未經取代之直鏈或支鏈C2 至C60 亞炔基；經取代或未經取代之單環或多環C3 至C60 環亞烷基；經取代或未經取代之單環或多環C2 至C60 雜環亞烷基；經取代或未經取代之單環或多環C6 至C60 亞芳基；及經取代或未經取代之單環或多環C2 至C60 雜亞芳基所組成之群組；以及 R2至R8係與式1中定義相同。According to an embodiment of the present invention, Formula 1 is represented by the following Formula 4 or Formula 5: [Formula 4] [Formula 5] In Formula 4 and Formula 5, A and A' are each independently selected from: a direct bond; a substituted or unsubstituted linear or branched C 2 to C 60 alkylene group; substituted or unsubstituted a linear or branched C 2 to C 60 alkenylene group; a substituted or unsubstituted linear or branched C 2 to C 60 alkynylene group; a substituted or unsubstituted monocyclic or polycyclic C 3 To a C 60 cycloalkylene; substituted or unsubstituted monocyclic or polycyclic C 2 to C 60 heterocycloalkylene; substituted or unsubstituted monocyclic or polycyclic C 6 to C 60 adenine And a group consisting of a substituted or unsubstituted monocyclic or polycyclic C 2 to C 60 heteroarylene; and R 2 to R 8 are the same as defined in Formula 1.
根據本發明一實施例，式4和式5中的A及A’係各自獨立選自由：一直接鍵結；經取代或未經取代之單環或多環C6 至C60 亞芳基；及經取代或未經取代之單環或多環C2 至C60 雜亞芳基所組成之群組。According to an embodiment of the present invention, A and A' in Formula 4 and Formula 5 are each independently selected from: a direct bond; a substituted or unsubstituted monocyclic or polycyclic C 6 to C 60 arylene; And a group consisting of a substituted or unsubstituted monocyclic or polycyclic C 2 to C 60 heteroarylene group.
根據本發明一實施例，式4和式5中的A及A’係各自獨立為一直接鍵結；經取代或未經取代之C6 至C60 亞芳基；或經取代或未經取代之C6 至C60 雜亞芳基，且可再被C1 至C20 烷基或經取代或未經取代之單環或多環C6 至C20 芳基所取代。According to an embodiment of the invention, A and A' in Formula 4 and Formula 5 are each independently a direct bond; a substituted or unsubstituted C 6 to C 60 arylene; or substituted or unsubstituted The C 6 to C 60 heteroarylene group may be further substituted with a C 1 to C 20 alkyl group or a substituted or unsubstituted monocyclic or polycyclic C 6 to C 20 aryl group.
根據本發明一實施例，式4和式5中的A及A’ 係各自獨立為一直接鍵結、一亞苯基、或一聯亞苯基。According to an embodiment of the present invention, A and A' in Formula 4 and Formula 5 are each independently a direct bond, a phenylene group, or a biphenylene group.
根據本發明一實施例，式1可選自由下列化合物。
根據本發明一實施例，式1可選自由下列化合物。
上述化合物可由下述製備例所製備。代表性實施例將於下方製備例中描述，但視需要可增加或排除取代基，且取代基的位置可變化。此外，基於習知技術領域中的技藝，可變化起始材料、反應物、反應條件等。The above compounds can be produced by the following preparations. Representative examples will be described in the preparations below, but substituents may be added or excluded as desired, and the positions of the substituents may vary. Furthermore, starting materials, reactants, reaction conditions, and the like can be varied based on the skill in the art.
例如，式1之化合物中，核心結構可由下反應式1或2所製備，取代基可由本技術領域中習知方法鍵結，且取代基的種類和位置、取代基的數目可根據習知技術而變化。 [反應式1][反應式2] For example, in the compound of Formula 1, the core structure can be prepared by the following Reaction Formula 1 or 2, and the substituent can be bonded by a method known in the art, and the kind and position of the substituent, the number of substituents can be according to the prior art. And change. [Reaction formula 1] [Reaction formula 2]
具體製備方法將於下方製備例詳述。The specific preparation method will be described in detail in the following preparation examples.
本發明另一實施例提供一種包含上述式1化合物之有機發光裝置。詳細而言，根據本發明之有機發光裝置包括：一正極；一負極；以及一或多層有機材料層，設於該正極與該負極之間；且該一或多層有機材料層包括式1之化合物。Another embodiment of the present invention provides an organic light-emitting device comprising the compound of the above formula 1. In detail, an organic light-emitting device according to the present invention includes: a positive electrode; a negative electrode; and one or more organic material layers disposed between the positive electrode and the negative electrode; and the one or more organic material layers include the compound of Formula 1. .
圖1至圖3繪示根據本發明實施例有機發光裝置之電極和有機材料層之堆疊結構。然而，本發明之範疇並不限於該些圖示，本技術領域中習知的有機發光裝置之結構可應用於本發明。1 to 3 illustrate a stacked structure of an electrode and an organic material layer of an organic light-emitting device according to an embodiment of the present invention. However, the scope of the present invention is not limited to the illustrations, and the structure of an organic light-emitting device known in the art can be applied to the present invention.
根據圖1，有機發光裝置中，基板100上依序堆疊正極200、有機材料層300、及負極400。然而，有機發光裝置之結構不限於此，且如圖2所示，有機發光裝置中，亦可為依序堆疊負極、有機材料層、和正極。According to FIG. 1, in the organic light-emitting device, the positive electrode 200, the organic material layer 300, and the negative electrode 400 are sequentially stacked on the substrate 100. However, the structure of the organic light-emitting device is not limited thereto, and as shown in FIG. 2, in the organic light-emitting device, the negative electrode, the organic material layer, and the positive electrode may be sequentially stacked.
圖3為複數層之有機材料層之實施例，根據圖3之有機發光裝置包含電洞注入層301、電洞傳輸層302、發光層303、電洞阻擋層304、電子傳輸層305及電子注入層306。然而，本發明之範疇不限於上述堆疊結構，若有需要可省略有機發光層以外的其他層，亦可添加其他所需功能層。3 is an embodiment of a plurality of layers of organic material layers. The organic light-emitting device according to FIG. 3 includes a hole injection layer 301, a hole transport layer 302, a light-emitting layer 303, a hole barrier layer 304, an electron transport layer 305, and electron injection. Layer 306. However, the scope of the present invention is not limited to the above-described stacked structure, and other layers than the organic light-emitting layer may be omitted if necessary, and other desired functional layers may be added.
除了ㄧ或多層之有機材料層需包含式1之化合物，根據本發明之有機發光裝置可由本技術領域中習知材料和方法所製造。The organic light-emitting device according to the present invention can be produced by materials and methods well known in the art, except that the organic material layer of the layer or layers needs to contain the compound of the formula 1.
式1之化合物可單獨組成有機發光裝置中一或多層之有機材料層。然而，若有需要，式1之化合物可和其他材料混合以組成有機材料層。The compound of Formula 1 may independently constitute one or more layers of organic materials in the organic light-emitting device. However, if desired, the compound of Formula 1 can be combined with other materials to form a layer of organic material.
式1之化合物可使用作為有機發光裝置中的電洞注入材料、電洞傳輸材料、發光材料、電洞阻擋材料、電子傳輸材料、電子注入材料等。The compound of Formula 1 can be used as a hole injecting material, a hole transporting material, a light emitting material, a hole blocking material, an electron transporting material, an electron injecting material, or the like in an organic light-emitting device.
例如，根據本發明實施例之化合物可用作為有機發光裝置中的電子注入層、電子傳輸層、或同時注入及傳輸電子層之材料。For example, a compound according to an embodiment of the present invention can be used as an electron injecting layer, an electron transporting layer, or a material for simultaneously injecting and transporting an electron layer in an organic light-emitting device.
此外，根據本發明實施例之化合物可用作為有機發光裝置中的發光層之材料，尤其，該化合物可單獨作為發光材料、及發光層之主體材料或摻雜劑材料。Further, the compound according to the embodiment of the present invention can be used as a material of the light-emitting layer in the organic light-emitting device, and in particular, the compound can be used alone as a light-emitting material, and a host material or a dopant material of the light-emitting layer.
此外，根據本發明之化合物可作為有機發光裝置中的磷光主體材料，在此情況下，根據本發明之化合物與一磷光摻雜劑共同存在。Furthermore, the compounds according to the invention can be used as phosphorescent host materials in organic light-emitting devices, in which case the compounds according to the invention are present together with a phosphorescent dopant.
此外，根據本發明之化合物可作為有機發光裝置中的電洞阻擋層的材料。Further, the compound according to the present invention can be used as a material for a hole blocking layer in an organic light-emitting device.
根據本發明之有機發光裝置，下方將說明除了式1之化合物以外的材料，不過這些材料僅供釋義而非用於限制本發明範疇，並可由本技術領域中已知的材料替換。In accordance with the organic light-emitting device of the present invention, materials other than the compound of Formula 1 will be described below, but these materials are for illustrative purposes only and are not intended to limit the scope of the present invention, and may be replaced by materials known in the art.
正極的材料可使用具有相對高功函數的材料，可使用透明導電氧化物、金屬或導電聚合物等。As the material of the positive electrode, a material having a relatively high work function can be used, and a transparent conductive oxide, a metal or a conductive polymer or the like can be used.
負極的材料可使用具有相對低功函數的材料，可使用金屬、金屬氧化物、或導電聚合物等。As the material of the negative electrode, a material having a relatively low work function can be used, and a metal, a metal oxide, a conductive polymer or the like can be used.
電洞注入材料亦可使用習知的電洞注入材料，可以使用鈦菁化合物，如美國專利號No.4,356,429中揭露的鈦菁銅(copper phthalocyanine)；或starburst型胺衍生物，如文獻[Advanced Material, 6, p. 677 (1994)]所述，例如TCTA、m-MTDATA、m-MTDAPB、聚苯胺/十二烷基苯磺酸(Pani/DBSA)或聚(3,4-乙烯二氧噻吩)/聚(4-苯乙烯磺酸) (PEDOT/PSS)(其為可溶性導電高分子)、聚苯胺/樟腦磺酸(Pani/CSA)或聚苯胺/聚(4-苯乙烯磺酸) (PANI/PSS)等。The hole injecting material may also use a conventional hole injecting material, and a phthalocyanine compound such as copper phthalocyanine disclosed in U.S. Patent No. 4,356,429; or a starburst type amine derivative such as the literature [Advanced] may be used. Material, 6, p. 677 (1994)], such as TCTA, m-MTDATA, m-MTDAPB, polyaniline/dodecylbenzenesulfonic acid (Pani/DBSA) or poly(3,4-ethylenedioxygen) Thiophene)/poly(4-styrenesulfonic acid) (PEDOT/PSS) (which is a soluble conductive polymer), polyaniline/camphorsulfonic acid (Pani/CSA) or polyaniline/poly(4-styrenesulfonic acid) (PANI/PSS), etc.
電洞傳輸材料可使用砒唑林衍生物、芳胺類衍生物、二苯乙烯衍生物、三苯二胺衍生物等，且亦可使用低分子量材料或高分子材料。As the hole transporting material, an oxazoline derivative, an arylamine derivative, a stilbene derivative, a triphenylenediamine derivative or the like can be used, and a low molecular weight material or a polymer material can also be used.
電子傳輸材料可使用噁二唑衍生物、蒽醌二甲烷(anthraquinodimethane)及其衍生物、苯醌及其衍生物、萘醌及其衍生物、蒽醌及其衍生物、四氰基蒽醌二甲烷及其衍生物、芴酮衍生物、二苯基二氰基乙烯及其衍生物、二苯醌衍生物、8-羥基喹啉之金屬複合物及其衍生物，且亦可使用低分子量材料和高分子材料。The electron transporting material may use an oxadiazole derivative, anthraquinodimethane and its derivatives, benzoquinone and its derivatives, naphthoquinone and its derivatives, anthracene and its derivatives, tetracyanoquinone Methane and its derivatives, anthrone derivatives, diphenyldicyanoethylene and its derivatives, diphenylguanidine derivatives, metal complexes of 8-hydroxyquinoline and derivatives thereof, and low molecular weight materials can also be used. And polymer materials.
電子注入材料可為例如本技術領域中常用的LiF，但本發明不限於此。The electron injecting material may be, for example, LiF commonly used in the art, but the invention is not limited thereto.
發光材料可使用紅色、綠色、或藍色發光材料，若有需要可混合兩種以上的發光材料來使用。此外，亦可使用螢光材料作為發光材料，但也可使用磷光材料。可單獨使用ㄧ種材料作為發光材料，該材料可藉由將各自由正極和負極注入之電洞和電子結合以發出光線；但也可以使用主體材料和摻雜劑材料，其共同作用而發光。The luminescent material may be a red, green, or blue luminescent material, and if necessary, two or more luminescent materials may be mixed and used. Further, a fluorescent material may be used as the luminescent material, but a phosphorescent material may also be used. The cerium material may be used alone as a luminescent material which can emit light by combining holes and electrons each injected from the positive electrode and the negative electrode; however, it is also possible to use a host material and a dopant material, which together act to emit light.
當根據本發明之化合物作為磷光主體材料時，習知可做為磷光摻雜劑材料者可共同使用。When the compound according to the present invention is used as a phosphorescent host material, it can be used as a phosphorescent dopant material.
例如，可使用由LL’MX、LL’L”M、LMXX’ 、L2 MX、及L3 M所示之磷光摻雜劑材料，但本發明不限於這些例子。For example, use may be made LL'MX, LL'L "M, LMXX ' , L 2 MX, and the phosphorescent dopant material shown L 3 M, but the present invention is not limited to these examples.
於此，L、L’、L”、X、及X’為與彼此不同之雙配位基配體，且M為形成八面體複合物之金屬。Here, L, L', L", X, and X' are bi-ligand ligands different from each other, and M is a metal forming an octahedral composite.
M可為銥、鉑、鋨等。M may be ruthenium, platinum, rhodium or the like.
L為陰離子性、雙配位基配體，藉由sp2 碳和雜原子配位於M，且X可執行抓電子或電洞的功能。L的非限制實施例包括2-(1-萘基)苯並唑、(2-苯基噁唑)、(2-苯基苯並噻唑)、(7,8-苯並喹啉)、(噻吩並吡啶) 、苯基吡啶、苯並噻吩吡啶、3-甲氧基-2-苯基吡啶、噻吩吡啶(thienylpyrizine)、甲苯基吡啶等。X的非限制實施例包含乙醯丙酮(acac)、六氟乙醯丙酮、亞柳基(salicylidene)、吡啶甲酸(picolinate)、8-羥基喹啉等。L is an anionic, didentate ligand, which is coordinated to M by sp 2 carbon and a hetero atom, and X can perform the function of trapping electrons or holes. Non-limiting examples of L include 2-(1-naphthyl)benzoxazole, (2-phenyloxazole), (2-phenylbenzothiazole), (7,8-benzoquinoline), Thiophenepyridine), phenylpyridine, benzothiophenepyridine, 3-methoxy-2-phenylpyridine, thienopyrizine, tolylpyridine, and the like. Non-limiting examples of X include acetamidine (acac), hexafluoroacetamidine, salicylidene, picolinate, 8-hydroxyquinoline, and the like.
更多具體範例如下所示，但本發明不限於這些範例。 More specific examples are shown below, but the invention is not limited to these examples.
接著，本發明將透過這些實施例加以詳述，但這些僅供解釋本發明而非用以限制本發明之範疇。The invention is further described in detail by the examples, but these are intended to be illustrative only and not to limit the scope of the invention.
＜< 實施例Example ＞>
＜ 製備例 1＞ 製備化合物 1-1-18 < Preparation Example 1> Preparation of Compound 1-1-18
在一單頸圓底燒瓶中，取乙基-o -磺醯基乙醯羥胺 (13.26 g, 46.47 mmol)溶於12 mL之1,4-二惡烷，然後將此反應溶液維持在0°C。緩慢逐滴添加過氯酸 (70%, 5.40 mL)，於維持該溫度下作用2分鐘，然後將此反應混合物攪拌5分鐘。待混合溶液中的反應終止，利用 H2 O/醚進行萃取並以MgSO4 乾燥，然後進行過濾。在減壓下蒸餾後得到固體化合物1-1 (9.33 g, 93%)。 In a single-necked round bottom flask, ethyl- o -sulfonylacetamide (13.26 g, 46.47 mmol) was dissolved in 12 mL of 1,4-dioxane, and the reaction solution was maintained at 0 °. C. Perchloric acid (70%, 5.40 mL) was slowly added dropwise, maintained at this temperature for 2 minutes, and then the reaction mixture was stirred for 5 minutes. The reaction in the mixed solution was terminated, extracted with H 2 O/ether and dried over MgSO 4 and then filtered. The solid compound 1-1 (9.33 g, 93%) was obtained after distillation under reduced pressure.
製備化合物Preparation of compounds 2-12-1
在一雙頸圓底燒瓶中，取四溴甲烷(42.2 g, 127.25 mmol)及三苯基膦(68.4 g, 260.88 mmol)於氮氣環境下完全溶解於500 mL之二氯甲烷 ，然後將此反應溶液維持在0°C下攪拌30分鐘。之後，緩慢逐滴添加喹啉-2-甲醛(10 g, 63.63 mmol)，作用10分鐘，然後將此反應溶液維持在0°C下攪拌1小時。待反應終止，利用二氯甲烷/H2 O萃取該反應混合物並以MgSO4 乾燥，然後進行過濾。將該混合物濃縮，然後使用己烷並過濾，以製造出固體產物 (19.5 g, 62.3 mmol, 98%)，將該固體產物完全溶於200 mL之四氫呋喃，接著在溫度維持於-78°C下緩慢添加KOtBu (118 g, 1.06 mol) 。之後，添加100 ML鹵水(brine)，將該反應混合物冷卻至室溫，待反應終止，利用***/H2 O萃取該反應混合物並以MgSO4 乾燥，然後進行過濾。將該混合物濃縮，然後使用己烷製造出一固體，將該固體過濾後得到乳白色固體化合物2-1 (14.2 g, 98%)。In a double neck round bottom flask, tetrabromomethane (42.2 g, 127.25 mmol) and triphenylphosphine (68.4 g, 260.88 mmol) were completely dissolved in 500 mL of dichloromethane under nitrogen, and then the reaction solution was taken. Stir at 0 ° C for 30 minutes. Thereafter, quinoline-2-carbaldehyde (10 g, 63.63 mmol) was slowly added dropwise for 10 minutes, and then the reaction solution was stirred at 0 ° C for 1 hour. After the reaction was terminated, the reaction mixture was extracted with dichloromethane / H 2 O and dried over MgSO 4 and then filtered. The mixture was concentrated, then hexanes was used and filtered to give a solid product (19.5 g, 62.3 mmol, 98%). The solid product was completely dissolved in 200 mL of tetrahydrofuran and then maintained at -78 °C. Add KOtBu (118 g, 1.06 mol) slowly. After that, 100 ML of brine was added, and the reaction mixture was cooled to room temperature. After the reaction was terminated, the mixture was extracted with diethyl ether/H 2 O and dried over MgSO 4 and then filtered. The mixture was concentrated, then a solid was obtained using hexane, and the solid was filtered to afford Compound 2-1 (14.2 g, 98%).
製備化合物Preparation of compounds 2-22-2
在一單頸圓底燒瓶中，取化合物1-1 (10 g, 46.45 mmol)完全溶解於50 mL二氯甲烷，然後將此反應溶液維持在0°C。取化合物2-1 (9.70 g, 41.81 mmol) 完全溶解於50 mL二氯甲烷，將該反應溶液緩慢逐滴添加至前述單頸圓底燒瓶中。將該混合物攪拌約10分鐘後，加入300 mL***，再將該反應混合物攪拌30分鐘。製造出白色固體，經過濾、以乙酸乙酯/甲醇再結晶後，得到白色固體化合物2-2 (15.7 g, 88%)。In a one-necked round bottom flask, Compound 1-1 (10 g, 46.45 mmol) was dissolved in 50 mL of dichloromethane, and then the reaction solution was maintained at 0 °C. Compound 2-1 (9.70 g, 41.81 mmol) was completely dissolved in 50 mL of dichloromethane, and the reaction solution was slowly added dropwise to the above-mentioned single-necked round bottom flask. After the mixture was stirred for about 10 minutes, 300 mL of diethyl ether was added and the reaction mixture was stirred for 30 minutes. A white solid was obtained, which was crystallised from ethyl acetate/methanol.
製備化合物Preparation of compounds 2-32-3
取6 g之K2 CO3 置入一單頸圓底燒瓶中，將化合物2-2 (10 g, 26.09 mmol)溶於10 mL二甲基甲醯胺後，緩慢逐滴添加至該單頸圓底燒瓶中。於室溫下攪拌該混合物約6小時，然後利用二氯甲烷/H2 O萃取，以硫酸鎂乾燥，然後過濾。將產物濃縮後，利用管柱層析分離(SiO2 , 二氯甲烷)，以得到白色固體化合物2-3 (6.1 g, 95%)。 6 g of K 2 CO 3 was placed in a single-necked round bottom flask, and compound 2-2 (10 g, 26.09 mmol) was dissolved in 10 mL of dimethylformamide and slowly added dropwise to the single neck. In a round bottom flask. The mixture was stirred at room temperature for about 6 hours, then extracted with dichloromethane / H 2 O, dried over magnesium sulfate and filtered. After the product was concentrated by column chromatography (SiO 2, dichloromethane) to give a white solid compound 2-3 (6.1 g, 95%) .
製備化合物Preparation of compounds 1-1-181-1-18
在一單頸圓底燒瓶中，取化合物2-3 (10 g, 40.47 mmol)於氮氣環境下溶於無水四氫呋喃(50 ml)，然後將反應溶液冷卻至-78°C。取正丁基鋰 (2.5 M溶於己烷) (21 ml, 52.61 mmol)緩慢逐滴添加至該反應溶液，然後將該反應混合物攪拌1小時。取氯二苯基膦(11.61 ml, 52.61 mol)逐滴添加至該溶液，然後將該反應混合物於室溫下攪拌12小時。將該反應混合物以二氯甲烷/H2 O萃取，然後於減壓下蒸餾。將該反應混合物溶於二氯甲烷 (250 ml)，然後將該反應溶液連同20 ml之30% H2 O2 水溶液於室溫下攪拌12小時。將該反應混合物以二氯甲烷/H2 O萃取，經濃縮後之混合物利用管柱層析分離 (SiO2 , 二氯甲烷: 甲醇 = 25 : 1)，以得到黃色固體化合物1-1-18 (4.03 g, 27%)。In a one-neck round bottom flask, compound 2-3 (10 g, 40.47 mmol) was dissolved in anhydrous tetrahydrofuran (50 ml) under nitrogen atmosphere, and then the reaction solution was cooled to -78 °C. N-Butyllithium (2.5 M in hexane) (21 ml, 52.61 mmol) was slowly added dropwise to the reaction solution, and then the reaction mixture was stirred for 1 hour. Chlorodiphenylphosphine (11.61 ml, 52.61 mol) was added dropwise to the solution, and the reaction mixture was stirred at room temperature for 12 hours. The reaction mixture was extracted with dichloromethane / H 2 O and then distilled under reduced pressure. The reaction mixture was dissolved in dichloromethane (250 ml), then the reaction solution was stirred together with 20 ml of 30% aqueous H 2 O 2 at room temperature for 12 hours. The reaction mixture was extracted with dichloromethane / H 2 O, the mixture was concentrated by the use of column chromatography (SiO 2, dichloromethane: methanol = 25: 1), to give a yellow solid compound 1-1-18 (4.03 g, 27%).
＜ 製備例 2＞ 製備化合物 1-1-86 < Preparation Example 2> Preparation of Compound 1-1-86
製備化合物Preparation of compounds A-1A-1
在一單頸圓底燒瓶中，混合(9,9-二甲基-9H-芴-2-基)硼酸(25.9 g, 0.108 mol)、1-溴-2-硝基苯(20 g, 0.099 mol)、四(三苯基膦) 鈀(5.7 g, 4.95 mmol)、碳酸鉀(27.3 g, 0.198 mol)、及四氫呋喃(250 ml)/H2 O (50 ml)得到一混合物，將其回流並攪拌24小時。移除水相層，將該有機層以MgSO4 乾燥。將該有機層濃縮後以管柱層析(SiO2 , 己烷 : 二氯甲烷 = 2 : 1)分離，得到黃色固體化合物A-1 (21 g, 61%)。In a single neck round bottom flask, mix (9,9-dimethyl-9H-indol-2-yl)boronic acid (25.9 g, 0.108 mol), 1-bromo-2-nitrobenzene (20 g, 0.099) Mol), tetrakis(triphenylphosphine)palladium (5.7 g, 4.95 mmol), potassium carbonate (27.3 g, 0.198 mol), and tetrahydrofuran (250 ml) / H 2 O (50 ml) to give a mixture and reflux Stir for 24 hours. Removing the aqueous layer, the organic layer was dried MgSO 4. The organic layer was concentrated by column chromatography (of SiO 2, hexane: dichloromethane = 2: 1) to obtain a yellow solid compound A-1 (21 g, 61 %).
製備化合物Preparation of compounds A-2A-2
在一單頸圓底燒瓶中，混合化合物1-1 (20 g, 0.0634 mmol)、三苯基膦(49.8 g, 0.190 mol)、及鄰二氯苯 (300 ml) 得到一混合物，將其回流並於氮氣環境下攪拌18小時。在減壓下蒸餾移除o-DCB，以管柱層析(SiO2 , 己烷 : 二氯甲烷 = 3: 1)分離，得到白色固體化合物A-2 (6.6 g, 36%)。In a one-neck round bottom flask, compound 1-1 (20 g, 0.0634 mmol), triphenylphosphine (49.8 g, 0.190 mol), and o-dichlorobenzene (300 ml) were mixed to obtain a mixture, which was refluxed. It was stirred under a nitrogen atmosphere for 18 hours. O-DCB removed by distillation under reduced pressure, purified by column chromatography (SiO 2, hexane: dichloromethane = 3: 1) to obtain a white solid compound A-2 (6.6 g, 36 %).
製備化合物Preparation of compounds 1-1-861-1-86
在一單頸圓底燒瓶中，混合化合物2-3 (6.0 g, 24.28 mmol)、化合物A-2 (6.19 g, 21.85 mmol)、Cu (0.15 g, 2.43 mmol)、18-冠-6-醚 (0.64 g, 2.43 mmol)、 碳酸鉀(10.1 g, 72.84 mmol)、及鄰二氯苯(80 ml) 得到一混合物，將其回流並於氮氣環境下攪拌24小時。在減壓下蒸餾移除鄰二氯苯，以管柱層析(SiO2 , 己烷 : 二氯甲烷 = 4: 1)分離，得到白色固體化合物1-1-86 (6.2 g, 57%)。In a single neck round bottom flask, compound 2-3 (6.0 g, 24.28 mmol), compound A-2 (6.19 g, 21.85 mmol), Cu (0.15 g, 2.43 mmol), 18-crown-6-ether (0.64 g, 2.43 mmol), potassium carbonate (10.1 g, 72.84 mmol), and o-dichlorobenzene (80 ml) were obtained as a mixture, which was refluxed and stirred under nitrogen for 24 hours. In the removal of o-dichlorobenzene was distilled, under reduced pressure and separated by column chromatography (SiO 2, hexanes:: dichloromethane = 41) to give a white solid compound 1-1-86 (6.2 g, 57%) .
＜ 製備例 3＞ 製備化合物 1-1-37 < Preparation Example 3> Preparation of Compound 1-1-37
製備化合物Preparation of compounds 3-13-1
在一雙頸圓底燒瓶中，混合化合物2-3 (6.0 g, 24.28 mmol)、雙（頻哪醇）二硼(bis(pinacolato)diboron) (7.4 g, 28.14 mmol)、醋酸鉀(4.77 g, 48.56 mmol)、 PdCl2 (dppf) (0.8 g, 1.21 mmol)、及1,4-二惡烷(120 ml) 得到一混合溶液，將其回流並於氮氣環境下攪拌3小時。 將該反應混合物冷卻至室溫，以二氯甲烷/H2 O萃取並以硫酸鎂乾燥，然後過濾。混合物經濃縮後，使用己烷以製造一固體，過濾該固體後得到乳白色固體化合物3-1 (6.1 g, 86%)。In a double necked round bottom flask, compound 2-3 (6.0 g, 24.28 mmol), bis(pinacolato)diboron (7.4 g, 28.14 mmol), potassium acetate (4.77 g) A mixed solution of 48.56 mmol), PdCl 2 (dppf) (0.8 g, 1.21 mmol), and 1,4-dioxane (120 ml) was refluxed and stirred under nitrogen for 3 hours. The reaction mixture was cooled to room temperature, extracted with dichloromethane / H 2 O and dried over magnesium sulfate. After the mixture was concentrated, hexane was used to give a solid, and the solid was filtered to afford compound 3-1 (6.1 g, 86%).
製備化合物Preparation of compounds 1-1-371-1-37
在一雙頸圓底燒瓶中，混合化合物3-1 (6.0 g, 20.40 mmol)、2-溴-4,6-二苯基嘧啶(6.98 g, 22.44 mmol)、醋酸鉀(5.64 g, 40.8 mmol)、四(三苯基膦) 鈀(1.18 g, 1.02 mmol)及甲苯/乙醇(EtOH)/H2 O (60 ml/12 ml/12 ml) 得到一混合溶液，將其回流並於氮氣環境下攪拌12小時。將反應混合物中的溶劑濾出，依序以100 ml甲苯、150 ml己烷、及150 ml甲醇清洗，以得到白色固體化合物1-1-37 (7.1 g, 88%)。In a double necked round bottom flask, compound 3-1 (6.0 g, 20.40 mmol), 2-bromo-4,6-diphenylpyrimidine (6.98 g, 22.44 mmol), potassium acetate (5.64 g, 40.8 mmol) , tetrakis(triphenylphosphine)palladium (1.18 g, 1.02 mmol) and toluene/ethanol (EtOH)/H 2 O (60 ml/12 ml/12 ml) to obtain a mixed solution, which was refluxed and placed in a nitrogen atmosphere. Stir under 12 hours. The solvent in the reaction mixture was filtered, washed with EtOAc EtOAcjjjjjjj
＜< 製備例Preparation example 4＞4> 製備化合物Preparation of compounds 1-1-631-1-63
製備化合物Preparation of compounds 3-23-2
在一單頸圓底燒瓶中，混合化合物3-1 (6.0 g, 20.40 mmol)、1-碘-4-溴苯 (6.35 g, 22.44 mol)、碳酸鉀(5.64 g, 40.8 mmol)、Pd(PPh3 )4 (1.18 g, 1.02 mmol)、及甲苯/乙醇/H2 O (60 ml/12 ml/12 ml) 得到一混合溶液，將其回流並攪拌6小時。將反應混合物中的溶劑濾出，依序以100 ml甲苯、150 ml己烷、及150 ml甲醇清洗，以得到白色固體化合物3-2 (4.0 g, 61%)。In a one-neck round bottom flask, compound 3-1 (6.0 g, 20.40 mmol), 1-iodo-4-bromobenzene (6.35 g, 22.44 mol), potassium carbonate (5.64 g, 40.8 mmol), Pd ( PPh 3 ) 4 (1.18 g, 1.02 mmol), and toluene/ethanol/H 2 O (60 ml / 12 ml / 12 ml) gave a mixed solution which was refluxed and stirred for 6 hours. The solvent in the reaction mixture was filtered, washed with 100 ml of toluene, 150 ml of hexane, and 150 ml of methanol to give white solid compound 3-2 (4.0 g, 61%).
製備化合物Preparation of compounds 1-1-631-1-63
在一雙頸圓底燒瓶中，混合化合物3-2 (4.0 g, 12.38 mmol)、[1,1':3',1''-三聯苯基]-5'-基-硼酸(3.73 g, 13.61 mmol)、碳酸鉀(3.42 g, 24.76 mmol)、四(三苯基膦) 鈀(0.72 g, 0.62 mmol)、及甲苯/乙醇/H2 O (40 ml/8 ml/8 ml) 得到一混合溶液，將其回流並於氮氣環境下攪拌12小時。將反應混合物中的溶劑濾出，依序以50 ml甲苯、80 ml己烷、及80 ml甲醇清洗，以得到白色固體化合物1-1-63 (5.4 g, 93%)。In a double necked round bottom flask, compound 3-2 (4.0 g, 12.38 mmol), [1,1':3',1''-triphenyl]-5'-yl-boronic acid (3.73 g, 13.61 mmol), potassium carbonate (3.42 g, 24.76 mmol), tetrakis(triphenylphosphine)palladium (0.72 g, 0.62 mmol), and toluene/ethanol/H 2 O (40 ml/8 ml/8 ml) The solution was mixed, refluxed and stirred under nitrogen for 12 hours. The solvent in the reaction mixture was filtered, washed with 50 ml of toluene, 80 ml of hexane, and 80 ml of methanol to give white solid compound 1-1-63 (5.4 g, 93%).
化合物3-2具有一型式，其中在式2的核心結構中，於R1位置溴苯基被取代。在製備例4中，化合物3-2的溴(Br)經由三聯苯基取代，以製備出化合物1-1-63。Compound 3-2 has a type in which a bromophenyl group is substituted at the R1 position in the core structure of Formula 2. In Preparation Example 4, bromine (Br) of Compound 3-2 was substituted with a terphenyl group to prepare Compounds 1-1-6.
例如，本技術領域中具有通常知識者可以修飾製備例4，導入三聯苯基以外的取代基。當使用化合物3-2取代化合物2-3用以製備化合物1-1-18時，得到之化合物結構中，導入經二苯基磷取代之苯基(化合物1-1-196)。換言之，能夠製備出包含磷系取代基的化合物，其在式2之核心結構中具有亞芳基聯結基團。例如，化合物1-1-74及化合物1-1-139為包含磷系取代基的化合物，具有亞芳基聯結基團。For example, those skilled in the art can modify Preparation 4 to introduce a substituent other than a terphenyl group. When Compound 3-2 is used instead of Compound 2-3 to prepare Compound 1-1-18, a phenyl group substituted with diphenylphosphine (Compound 1-1-1) is introduced into the structure of the obtained compound. In other words, a compound containing a phosphorus-based substituent having an arylene bond group in the core structure of Formula 2 can be prepared. For example, the compound 1-1-174 and the compound 1-1-139 are compounds containing a phosphorus-based substituent and have an arylene bond group.
此外，藉由利用製備例1之化合物2-3取代製備例4之化合物3-2，如三聯苯基之取代基可以直接導入式2之核心結構中。Further, by substituting the compound 2-3 of Preparation Example 1 for the compound 3-2 of Preparation Example 4, a substituent such as a terphenyl group can be directly introduced into the core structure of Formula 2.
＜ 製備例 5＞ 製備化合物 1-1-180 < Preparation Example 5> Preparation of Compound 1-1-180
在一雙頸圓底燒瓶中，混合化合物3-2 (5.0 g, 15.47 mmol)、3,5-二(9H-咔唑基-9-基)苯基)硼酸 (7.7 g, 17.02 mmol)、K2 CO3 (4.28 g, 30.94 mmol)、四(三苯基膦)鈀(0.89 g, 0.77 mmol)、及甲苯/乙醇/H2 O (100 ml/20 ml/20 ml) 得到一混合溶液，將其回流並於氮氣環境下攪拌12小時。 將該反應混合物冷卻至室溫，利用二氯甲烷/H2 O萃取並以硫酸鎂乾燥，然後過濾。該產物經濃縮後，接著用管柱層析(SiO2 , 己烷: 二氯甲烷 = 2 : 1)分離，以得到白色固體化合物1-1-180 (6.64 g, 66%)。In a double neck round bottom flask, compound 3-2 (5.0 g, 15.47 mmol), 3,5-bis(9H-carbazolyl-9-yl)phenyl)boronic acid (7.7 g, 17.02 mmol), a mixed solution of K 2 CO 3 (4.28 g, 30.94 mmol), tetrakis(triphenylphosphine)palladium (0.89 g, 0.77 mmol), and toluene/ethanol/H 2 O (100 ml/20 ml/20 ml) It was refluxed and stirred under a nitrogen atmosphere for 12 hours. The reaction mixture was cooled to room temperature, extracted with dichloromethane / H 2 O and dried over magnesium sulfate. After the product was concentrated, followed by column chromatographic separation (of SiO 2, hexanes: 1: methylene chloride = 2), to give a white solid compound 1-1-180 (6.64 g, 66%) .
＜ 製備例 6＞ 製備化合物 1-1-109 < Preparation Example 6> Preparation of Compound 1-1-109
製備化合物Preparation of compounds B-1B-1
在一雙頸圓底燒瓶中，混合2-溴-4,6-二苯基-1,3,5-三嗪(10.0 g, 32.03 mmol)、雙（頻哪醇）二硼(9.76 g, 38.44 mmol) 、醋酸鉀(6.29 g, 64.06 mmol)、PdCl2 dppf (dppf: 1,1'-雙(二苯基磷) 二茂鐵) (1.17 g, 1.60 mmol) 、及1,4-二惡烷(100 ml) 得到一混合溶液，將其回流並於氮氣環境下攪拌3小時。 將該反應混合物冷卻至室溫，以二氯甲烷/H2 O萃取並以硫酸鎂乾燥，然後過濾。混合物經濃縮後，使用己烷以製造一固體，過濾該固體後得到乳白色固體化合物B-1 (19.67 g, 83%)。In a double necked round bottom flask, 2-bromo-4,6-diphenyl-1,3,5-triazine (10.0 g, 32.03 mmol), bis(pinacol) diboron (9.76 g, 38.44 mmol), potassium acetate (6.29 g, 64.06 mmol), PdCl 2 dppf (dppf: 1,1'-bis(diphenylphosphino)ferrocene) (1.17 g, 1.60 mmol), and 1,4-two A mixed solution of methane (100 ml) was obtained, which was refluxed and stirred under nitrogen for 3 hr. The reaction mixture was cooled to room temperature, extracted with dichloromethane / H 2 O and dried over magnesium sulfate. After the mixture was concentrated, hexane was used to give a solid, and the solid was filtered to afford Compound Compound B-1 (19.67 g, 83%).
製備化合物Preparation of compounds 4-14-1
在一單頸圓底燒瓶中，混合化合物3-1 (8.0 g, 27.20 mmol)、1-碘-3-溴苯(8.46 g, 29.92 mmol) 、碳酸鉀(7.52 g, 54.5 mmol)、Pd(PPh3 )4 (1.57 g, 1.36 mmol) 、及甲苯/乙醇/H2 O (80 ml/16 ml/16 ml) 得到一混合溶液，將其回流並攪拌6小時。將反應混合物中的溶劑濾出，依序以100 ml甲苯、150 ml己烷、及150 ml甲醇清洗，以得到白色固體化合物4-1(5.0 g, 57%).In a single neck round bottom flask, compound 3-1 (8.0 g, 27.20 mmol), 1-iodo-3-bromobenzene (8.46 g, 29.92 mmol), potassium carbonate (7.52 g, 54.5 mmol), Pd ( PPh 3 ) 4 (1.57 g, 1.36 mmol), and toluene/ethanol/H 2 O (80 ml/16 ml/16 ml) gave a mixed solution which was refluxed and stirred for 6 hours. The solvent in the reaction mixture was filtered, washed with 100 ml of toluene, 150 ml of hexane, and 150 ml of methanol to give white solid compound 4-1 (5.0 g, 57%).
製備化合物Preparation of compounds 1-1-1091-1-109
在一雙頸圓底燒瓶中，混合化合物4-1 (5.0 g, 15.47 mmol)、2,4-二苯基-6-(4,4,5,5-四甲基-1,3,2-二氧硼烷-2-基)-1,3,5-三嗪(6.67 g, 18.56 mmol)、碳酸鉀 (4.28 g, 30.94 mmol)、四(三苯基膦)鈀(0.89 g, 0.77 mol) 、及甲苯/乙醇/H2 O (100 ml/20 ml/20 ml) 得到一混合溶液，將其回流並於氮氣環境下攪拌12小時。 將該反應混合物冷卻至室溫，利用二氯甲烷/H2 O萃取並以硫酸鎂乾燥，然後過濾。該產物經濃縮後，接著用管柱層析(SiO2 , 己烷: 二氯甲烷 = 4 : 1)分離，以得到白色固體化合物1-1-109 (6.0 g, 82%)。In a double necked round bottom flask, compound 4-1 (5.0 g, 15.47 mmol), 2,4-diphenyl-6-(4,4,5,5-tetramethyl-1,3,2) -dioxaborolan-2-yl)-1,3,5-triazine (6.67 g, 18.56 mmol), potassium carbonate (4.28 g, 30.94 mmol), tetrakis(triphenylphosphine)palladium (0.89 g, 0.77 Mol), and toluene/ethanol/H 2 O (100 ml/20 ml/20 ml) gave a mixed solution which was refluxed and stirred under nitrogen for 12 hours. The reaction mixture was cooled to room temperature, extracted with dichloromethane / H 2 O and dried over magnesium sulfate. After the product was concentrated, followed by column chromatography (SiO 2, hexanes: 1: methylene chloride = 4), to give a white solid compound 1-1-109 (6.0 g, 82%) .
＜ 製備例 7＞ 製備化合物 1-1-120 < Preparation Example 7> Preparation of Compound 1-1-120
製備化合物Preparation of compounds C-1C-1
在一單頸圓底燒瓶中，混合1,2-二環己酮(30.0 g, 0.374 mol)、苯肼鹽酸(phenylhydrazine hydrochloride)(77.37 g, 0.749 mol)、及乙醇(1,000 ml)，得到一混合物，在氮氣環境下緩慢逐滴添加硫酸(1.4 mL, 0.0374 mol)，然後將該反應混合物於60°C下攪拌4小時。將該溶液冷卻至室溫，經過濾後得到黃棕色固體 (69 g, 93%)。在一單頸圓底燒瓶中，混合該固體(68.9 g, 0.25 mol)及醋酸(700 ml) 得到一混合物，添加三氟乙酸(46.5 mL, 0.6 mol)，且該反應混合物於100°C下攪拌12小時。該溶液冷卻至室溫後，以醋酸和己烷清洗，經過濾後得到乳白色固體C-1 (27.3 g, 42%)。In a single neck round bottom flask, 1,2-dicyclohexanone (30.0 g, 0.374 mol), phenylhydrazine hydrochloride (77.37 g, 0.749 mol), and ethanol (1,000 ml) were mixed to obtain a The mixture was slowly added dropwise with sulfuric acid (1.4 mL, 0.0374 mol) under a nitrogen atmosphere, and then the mixture was stirred at 60 ° C for 4 hours. The solution was cooled to room temperature and filtered to give a brown brown solid. In a single neck round bottom flask, the solid (68.9 g, 0.25 mol) and acetic acid (700 ml) were mixed to give a mixture, trifluoroacetic acid (46.5 mL, 0.6 mol), and the reaction mixture was at 100 ° C Stir for 12 hours. After the solution was cooled to room temperature, it was washed with ethyl acetate and hexane, and filtered to give a white solid C-1 (27.3 g, 42%).
製備化合物Preparation of compounds C-2C-2
在一雙頸圓底燒瓶中，混合化合物C-1 (2.1 g, 0.0082 mol)、碘苯(2.5 g, 0.013 mol)、Cu (0.312 g, 0.0049)、18-冠-6-醚(0.433 g, 0.0016 mol)、碳酸鉀(3.397 g, 0.0246 mol)、及鄰二氯苯(20 ml) 得到一混合物，將其回流並於氮氣環境下攪拌12小時。將該反應混合物冷卻至室溫，以二氯甲烷/H2 O萃取並濃縮，以管柱層析(SiO2 , 己烷 : 乙酸乙酯 =10: 1)分離，得到白色固體化合物C-2 (1.76 g, 64%)。In a double neck round bottom flask, compound C-1 (2.1 g, 0.0082 mol), iodobenzene (2.5 g, 0.013 mol), Cu (0.312 g, 0.0049), 18-crown-6-ether (0.433 g) A mixture of 0.0016 mol), potassium carbonate (3.397 g, 0.0246 mol) and o-dichlorobenzene (20 ml) was refluxed and stirred under nitrogen for 12 hours. The reaction mixture was cooled to room temperature, dichloromethane / H 2 O and extracted and concentrated, purified by column chromatography (SiO 2, hexane: ethyl acetate = 10: 1) to obtain a white solid compound C-2 (1.76 g, 64%).
製備化合物Preparation of compounds 1-1-1201-1-120
在一單頸圓底燒瓶中，混合化合物4-1 (6.0 g, 24.28 mmol)、化合物C-2 (9.69 g, 29.14 mmol)、Cu (0.15 g, 2.43 mmol)、18-冠-6-醚 (0.64 g, 2.43 mmol) 、碳酸鉀(6.71 g, 48.56 mmol) 、及鄰二氯苯(60 ml) 得到一混合物，將其回流並於氮氣環境下攪拌24小時。在減壓下蒸餾移除 鄰二氯苯以管柱層析(SiO2 , 己烷 : 二氯甲烷 =3: 1)分離，得到白色固體化合物1-1-120 (6.7 g, 48%)。In a single neck round bottom flask, compound 4-1 (6.0 g, 24.28 mmol), compound C-2 (9.69 g, 29.14 mmol), Cu (0.15 g, 2.43 mmol), 18-crown-6-ether A mixture of (0.64 g, 2.43 mmol), potassium carbonate (6.71 g, 48.56 mmol) and o-dichlorobenzene (60 ml) was refluxed and stirred under nitrogen for 24 hours. The o-dichlorobenzene was removed by distillation under reduced pressure to give crystals (yield: SiO 2 , hexane : methylene chloride = 3:1) to afford white solid compound 1-1-120 (6.7 g, 48%).
＜ 製備例 8＞ 製備化合物 1-1-154 < Preparation Example 8> Preparation of Compound 1-1-154
製備化合物Preparation of compounds 5-15-1
在一單頸圓底燒瓶中，混合化合物2-3 (6.0 g, 24.28 mmol)、苯基硼酸(3.55 g, 29.14 mmol)、碳酸鉀(6.71 g, 48.56 mmol)、四(三苯基膦) 鈀(1.40 g, 1.21 mmol)、及甲苯/乙醇/H2 O (60 ml/12 ml/12 ml) 得到一混合物，將其回流並攪拌6小時。將反應混合物中的溶劑濾出，依序以50 ml甲苯、80 ml己烷、及80 ml甲醇清洗，以得到白色固體化合物5-1 (5.6 g, 95%)。In a single neck round bottom flask, compound 2-3 (6.0 g, 24.28 mmol), phenylboronic acid (3.55 g, 29.14 mmol), potassium carbonate (6.71 g, 48.56 mmol), tetrakis(triphenylphosphine) Palladium (1.40 g, 1.21 mmol), and toluene/ethanol/H 2 O (60 ml / 12 ml / 12 ml) gave a mixture which was refluxed and stirred for 6 hours. The solvent in the reaction mixture was filtered, washed with 50 ml of toluene, 80 ml of hexane, and 80 ml of methanol to give white solid compound 5-1 (5.6 g, 95%).
製備化合物Preparation of compounds 5-25-2
取100 mL之CHCl3 及br2 (2.1 mL, 40.94 mmol)置入一單頸圓底燒瓶中，將該反應混合物攪拌10分鐘，然後使溫度維持在0°C。取化合物5-1 (5 g, 20.47 mmol)溶於50 mL氯仿中，然後緩慢逐滴添加至該單頸圓底燒瓶中。約1小時後反應終止，利用二氯甲烷/H2 O萃取該產物並濃縮，然後以少量EA和己烷清洗，得到固體化合物5-2 (6.2 g, 94%)。100 mL of CHCl 3 and br 2 (2.1 mL, 40.94 mmol) were placed in a one-neck round bottom flask, and the reaction mixture was stirred for 10 minutes, and then the temperature was maintained at 0 °C. Compound 5-1 (5 g, 20.47 mmol) was dissolved in 50 mL of chloroform and then slowly added dropwise to the one-neck round bottom flask. After about 1 hour the reaction was terminated using dichloromethane / H 2 O The product was extracted and concentrated, then washed with a small amount of EA and hexane to obtain a solid compound 5-2 (6.2 g, 94%) .
製備化合物Preparation of compounds 1-1-1541-1-154
在一單頸圓底燒瓶中，混合化合物5-2 (6.0 g, 18.56 mmol)、 2,4-二苯基-6-(4,4,5,5-四甲基-1,3,2-二氧硼烷-2-基)-1,3,5-三嗪(8.0 g, 22.28 mmol)、碳酸鉀(5.13 g, 37.12 mmol) 、四(三苯基膦)鈀(1.07 g, 0.93 mmol)、及甲苯/乙醇/H2 O (60 ml/12 ml/12 ml) 得到一混合溶液，將其回流並於氮氣環境下攪拌12小時。 將該反應混合物冷卻至室溫，利用二氯甲烷/H2 O萃取並濃縮，接著用管柱層析(SiO2 , 己烷: 二氯甲烷 = 3 : 1)分離，以得到白色固體化合物1-1-154 (6.88 g, 78%).In a single neck round bottom flask, compound 5-2 (6.0 g, 18.56 mmol), 2,4-diphenyl-6-(4,4,5,5-tetramethyl-1,3,2 -dioxaborolan-2-yl)-1,3,5-triazine (8.0 g, 22.28 mmol), potassium carbonate (5.13 g, 37.12 mmol), tetrakis(triphenylphosphine)palladium (1.07 g, 0.93 Methyl), and toluene/ethanol/H 2 O (60 ml / 12 ml / 12 ml) gave a mixed solution which was refluxed and stirred under nitrogen for 12 hours. The reaction mixture was cooled to room temperature, extracted with dichloromethane/H 2 O and concentrated, and then purified by column chromatography (SiO 2 , hexane : methylene chloride = 3 : 1 ) to give white solid compound 1 -1-154 (6.88 g, 78%).
＜ 製備例 9＞ 製備化合物 1-1-186 < Preparation Example 9> Preparation of Compound 1-1-186
在一單頸圓底燒瓶中，混合化合物3-1 (6.0 g, 20.4 mmol)、化合物3-2 (7.9 g, 24.48 mmol)、碳酸鉀 (8.46 g, 61.2 mmol) 、四(三苯基膦)鈀(1.18 g, 1.02 mmol) 、及甲苯/乙醇/H2 O (60 ml/12 ml/12 ml) 得到一混合溶液，將其回流並於氮氣環境下攪拌12小時。 將該反應混合物冷卻至室溫，利用二氯甲烷/H2 O萃取並濃縮，接著用管柱層析(SiO2 , 己烷: 二氯甲烷 = 4 : 1)分離，以得到白色固體化合物1-1-186 (5.26 g, 64%)。In a single neck round bottom flask, compound 3-1 (6.0 g, 20.4 mmol), compound 3-2 (7.9 g, 24.48 mmol), potassium carbonate (8.46 g, 61.2 mmol), tetrakis(triphenylphosphine) Palladium (1.18 g, 1.02 mmol), and toluene/ethanol/H 2 O (60 ml / 12 ml / 12 ml) gave a mixed solution which was refluxed and stirred under nitrogen for 12 hours. The reaction mixture was cooled to room temperature, extracted with dichloromethane/H 2 O and concentrated, and then purified by column chromatography (SiO 2 , hexane : methylene chloride = 4 : 1 ) to give white solid compound 1 -1-186 (5.26 g, 64%).
＜ 製備例 10＞ 製備化合物 1-1-190 < Preparation Example 10> Preparation of Compound 1-1-190
在一單頸圓底燒瓶中，取化合物3-2 (10 g, 30.94 mmol)完全溶於 200 mL四氫呋喃，然後維持溫度於-78°C時緩慢逐滴添加正丁基鋰(6.6 mL, 32.04 mmol)。將反應混合物攪拌約30分鐘，然後緩慢逐滴添加氯三苯基矽烷(10.03 g, 34.03 mmol)，約1小時後反應終止，利用二氯甲烷/H2 O萃取並濃縮，接著用管柱層析(SiO2 , 己烷: 二氯甲烷 = 4 : 1)分離，以得到白色固體化合物1-1-190 (5.29 g, 34%)。In a single-necked round bottom flask, compound 3-2 (10 g, 30.94 mmol) was dissolved in 200 mL of tetrahydrofuran, and then n-butyllithium (6.6 mL, 32.04) was slowly added dropwise while maintaining the temperature at -78 °C. Mm). The reaction mixture was stirred for about 30 minutes, then chlorotriphenylnonane (10.03 g, 34.03 mmol) was slowly added dropwise, the reaction was quenched after about 1 hour, extracted with dichloromethane/H 2 O and concentrated, then It was isolated (SiO 2 , hexane : methylene chloride = 4 : 1) to afford white solid compound 1-1-190 (5.29 g, 34%).
＜ 製備例 11＞ 製備化合物 1-1-192 < Preparation Example 11> Preparation of Compound 1-1-192
在一單頸圓底燒瓶中，混合化合物3-1 (6.0 g, 20.4 mmol)、2,6-二溴吡啶(5.8 g, 24.48 mmol)、碳酸鉀(8.46 g, 61.2 mmol) 、四(三苯基膦)鈀(1.18 g, 1.02 mmol), and 、及甲苯/乙醇/H2 O (60 ml/12 ml/12 ml) 得到一混合溶液，將其回流並於氮氣環境下攪拌6小時。將該反應混合物冷卻至室溫，利用二氯甲烷/H2 O萃取並濃縮，接著用管柱層析(SiO2 , 己烷: 二氯甲烷 =2 : 1)分離，以得到白色固體化合物1-1-192 (6.60 g, 78%)。In a single neck round bottom flask, compound 3-1 (6.0 g, 20.4 mmol), 2,6-dibromopyridine (5.8 g, 24.48 mmol), potassium carbonate (8.46 g, 61.2 mmol), and four (three) Phenylphosphine)palladium (1.18 g, 1.02 mmol), and, and toluene/ethanol/H 2 O (60 ml / 12 ml / 12 ml) gave a mixed solution which was refluxed and stirred under nitrogen for 6 hours. The reaction mixture was cooled to room temperature, extracted with dichloromethane / H 2 O and concentrated, and then purified by column chromatography (SiO 2 , hexane : methylene chloride = 2 : 1 ) to give white solid compound 1 -1-192 (6.60 g, 78%).
＜ 製備例 12＞ 製備化合物 1-1-193 < Preparation Example 12> Preparation of Compound 1-1-193
在一單頸圓底燒瓶中，混合化合物2-3 (6.0 g, 24.28 mmol)、二([1,1'-聯苯基]-4-基)胺) (7.0 g, 21.85 mmol)、Cu (0.15 g, 2.43 mmol)、18-冠-6-醚(0.64 g, 2.43 mmol)、碳酸鉀(10.1 g, 72.84 mmol) 、及鄰二氯苯(80 ml) 得到一混合物，將其回流並於氮氣環境下攪拌24小時。在減壓下蒸餾移除鄰二氯苯，以管柱層析(SiO2 , 己烷 : 二氯甲烷 = 5: 1)分離，得到白色固體化合物1-1-193 (5.5 g, 46%).In a single neck round bottom flask, compound 2-3 (6.0 g, 24.28 mmol), bis([1,1'-biphenyl]-4-yl)amine (7.0 g, 21.85 mmol), Cu (0.15 g, 2.43 mmol), 18-crown-6-ether (0.64 g, 2.43 mmol), potassium carbonate (10.1 g, 72.84 mmol), and o-dichlorobenzene (80 ml). Stir under nitrogen for 24 hours. Distilled under reduced pressure to remove o-dichlorobenzene, by column chromatographic separation (SiO 2, hexanes: 1: methylene chloride = 5), to give a white solid compound 1-1-193 (5.5 g, 46%) .
＜ 製備例 13＞ 製備化合物 1-1-200 < Preparation Example 13> Preparation of Compound 1-1-200
在一單頸圓底燒瓶中，混合o-DCB (80 ml)、化合物2-3 (6.0 g, 24.28 mmol)、試劑(8.2 g, 21.85 mmol)、Cu (0.15 g, 2.43 mmol)、18-冠-6-醚(0.79 g, 2.43 mmol)及K2 CO3 (10.1 g, 72.84 mmol) 得到一混合物，將其回流並於氮氣環境下攪拌12小時。在減壓下蒸餾移除o-DCB，以管柱層析(SiO2 , 己烷 : MC = 4: 1)分離，得到白色固體化合物1-1-200 (10.8 g, 82%)。In a single neck round bottom flask, mix o-DCB (80 ml), compound 2-3 (6.0 g, 24.28 mmol), reagent (8.2 g, 21.85 mmol), Cu (0.15 g, 2.43 mmol), 18- crown-6 (0.79 g, 2.43 mmol) and K 2 CO 3 (10.1 g, 72.84 mmol) to give a mixture which was stirred and refluxed under nitrogen atmosphere for 12 hours. The o-DCB was removed by distillation under reduced pressure, and purified by column chromatography (SiO 2 , hexane : EtOAc = 4:1) to afford white solid compound 1-1-200 (10.8 g, 82%).
＜ 製備例 14＞ 製備化合物 1-1-201 < Preparation Example 14> Preparation of Compound 1-1-201
利用與製備例13中製備化合物1-1-200的方法相同的方式，除了使用N-(9,9-二甲基-9H-芴-3-基) 二苯並[b,d]呋喃-4-胺取代方法中的N-(9,9-二甲基-9H-芴-3-基) 二苯並[b,d]呋喃-2-胺，製備出一產物(10.1 g, 77%)。Using the same procedure as in the preparation of the compound 1-1-200 in Preparation 13, except that N-(9,9-dimethyl-9H-indol-3-yl)dibenzo[b,d]furan- N-(9,9-dimethyl-9H-indol-3-yl)dibenzo[b,d]furan-2-amine in the 4-amine substitution method to prepare a product (10.1 g, 77%) ).
＜ 製備例 15＞ 製備化合物 1-1-202 < Preparation Example 15> Preparation of Compound 1-1-202
利用與製備例13中製備化合物1-1-200的方法相同的方式，除了使用N-([1,1’-二甲基]-3-基)-9,9-二甲基-9H-芴-4-胺取代方法中的N-(9,9-二甲基-9H-芴-3-基) 二苯並[b,d]呋喃-2-胺，製備出一產物(10.4 g, 49%)。In the same manner as the method for producing the compound 1-1-200 in Preparation 13, except that N-([1,1'-dimethyl]-3-yl)-9,9-dimethyl-9H- was used. Preparation of a product (10.4 g, N-(9,9-dimethyl-9H-indol-3-yl)dibenzo[b,d]furan-2-amine in the oxime-4-amine substitution method 49%).
＜ 製備例 16＞ 製備化合物 1-1-203 < Preparation Example 16> Preparation of Compound 1-1-203
利用與製備例13中製備化合物1-1-200的方法相同的方式，除了使用N-(9,9’-螺二[芴]-3-基) 二苯並[b,d] 噻吩-2-胺取代方法中的N-(9,9-二甲基-9H-芴-3-基) 二苯並[b,d]呋喃-2-胺，製備出一產物(15.1 g, 55%)。The same procedure as in the preparation of the compound 1-1-200 in Preparation Example 13 except that N-(9,9'-spirobis[芴]-3-yl)dibenzo[b,d]thiophene-2 was used. - N-(9,9-dimethyl-9H-indol-3-yl)dibenzo[b,d]furan-2-amine in the amine substitution method to prepare a product (15.1 g, 55%) .
＜ 製備例 17＞ 製備化合物 1-1-204 < Preparation Example 17> Preparation of Compound 1-1-204
利用與製備例13中製備化合物1-1-200的方法相同的方式，除了使用N-(9,9'-螺二[芴]-3-基)二苯並[b,d]呋喃-2-胺取代方法中的N-(9,9-二甲基-9H-芴-3-基) 二苯並[b,d]呋喃-2-胺，製備出一產物(11.8 g, 44%)。The same procedure as in the preparation of the compound 1-1-200 in Preparation Example 13 except that N-(9,9'-spirobis[芴]-3-yl)dibenzo[b,d]furan-2 was used. - N-(9,9-dimethyl-9H-indol-3-yl)dibenzo[b,d]furan-2-amine in the amine substitution method to prepare a product (11.8 g, 44%) .
＜ 製備例 18＞ 製備化合物 1-1-206 < Preparation Example 18> Preparation of Compound 1-1-206
在一單頸圓底燒瓶中，混合o-DCB (80 ml) 、化合物2-3 (6.0 g, 24.28 mmol) 、試劑(8.9 g, 21.85 mmol)、Cu (0.15 g, 2.43 mmol) 、18-冠-6-醚(0.79 g, 2.43 mmol) 及K2 CO3 (10.1 g, 72.84 mmol) 得到一混合物，將其回流並於氮氣環境下攪拌12小時。在減壓下蒸餾移除o-DCB，以管柱層析(SiO2 , 己烷 : MC = 4: 1)分離，得到白色固體化合物1-1-206(8.4 g, 60%)。In a single neck round bottom flask, mix o-DCB (80 ml), compound 2-3 (6.0 g, 24.28 mmol), reagent (8.9 g, 21.85 mmol), Cu (0.15 g, 2.43 mmol), 18- A mixture of crown-6-ether (0.79 g, 2.43 mmol) and K 2 CO 3 (10.1 g, 72.84 mmol) was obtained, which was refluxed and stirred under nitrogen for 12 hours. The o-DCB was removed by distillation under reduced pressure, and purified by column chromatography (SiO 2 , hexane : EtOAc = 4:1) to afford white solid compound 1-1-206 (8.4 g, 60%).
＜ 製備例 19＞ 製備化合物 1-1-207 < Preparation Example 19> Preparation of Compound 1-1-207
在一單頸圓底燒瓶中，混合o-DCB (80 ml) 、化合物5-2 (10.0 g, 30.94 mmol) 、試劑(12.9 g, 34.04 mmol)、Cu (0.19 g, 3.09 mmol) 、18-冠-6-醚(1.0 g, 3.09 mmol) 及K2 CO3 (12.8 g, 92.82 mmol) 得到一混合物，將其回流並於氮氣環境下攪拌12小時。在減壓下蒸餾移除o-DCB，以管柱層析(SiO2 , 己烷 : MC = 3: 1)分離，得到白色固體化合物1-1-207 (14.8 g, 77%).In a single neck round bottom flask, mix o-DCB (80 ml), compound 5-2 (10.0 g, 30.94 mmol), reagent (12.9 g, 34.04 mmol), Cu (0.19 g, 3.09 mmol), 18- A mixture of crown-6-ether (1.0 g, 3.09 mmol) and K 2 CO 3 (12.8 g, 92.82 mmol) was obtained, which was refluxed and stirred under nitrogen for 12 hours. The o-DCB was removed by distillation under reduced pressure, and purified by column chromatography (SiO 2 , hexane : MC = 3: 1) to afford white solid compound 1-1-207 (14.8 g, 77%).
＜ 製備例 20＞ 製備化合物 1-1-208 < Preparation Example 20> Preparation of Compound 1-1-208
利用與製備例19中製備化合物1-1-207的方法相同的方式，除了使用N-(二苯並[b,d] 噻吩-2-基) 二苯並[b,d]呋喃-2-胺取代方法中的雙(二苯並[b,d] 噻吩-2-基)胺，製備出一產物(12.4 g, 66%)。The same procedure as in the preparation of the compound 1-1-207 in Preparation 19 except that N-(dibenzo[b,d]thiophen-2-yl)dibenzo[b,d]furan-2- was used. A product (12.4 g, 66%) was prepared from the bis(dibenzo[b,d]thiophen-2-yl)amine in the amine substitution procedure.
＜ 製備例 21＞ 製備化合物 1-1-210 < Preparation Example 21> Preparation of Compound 1-1-1-210
利用與製備例19中製備化合物1-1-207的方法相同的方式，除了使用N-(9,9-二甲基-9H-芴-3-基)二苯並[b,d]呋喃-2-胺取代方法中的雙(二苯並[b,d] 噻吩-2-基)胺，製備出一產物(13.6 g, 71%)。The same procedure as in the preparation of the compound 1-1-207 in Preparation 19 except that N-(9,9-dimethyl-9H-indol-3-yl)dibenzo[b,d]furan- A product (13.6 g, 71%) was prepared from the bis(dibenzo[b,d]thiophen-2-yl)amine in the 2-amine substitution procedure.
＜ 製備例 22＞ 製備化合物 1-1-213 < Preparation Example 22> Preparation of Compound 1-1-1-213
利用與製備例19中製備化合物1-1-207的方法相同的方式，除了使用N-(9,9'-螺二[芴]-2-基)二苯並[b,d]呋喃-2-胺取代方法中的雙(二苯並[b,d] 噻吩-2-基)胺，製備出一產物(12.1 g, 53%)。The same procedure as in the preparation of the compound 1-1-207 in Preparation 19 except that N-(9,9'-spirobis[芴]-2-yl)dibenzo[b,d]furan-2 was used. - A bis(dibenzo[b,d]thiophen-2-yl)amine in the amine substitution process to give a product (12.1 g, 53%).
化合物1-1-1至化合物1-1-216可基於製備例1至22，經由修改鍵結的取代基而製備出來。Compound 1-1-1 to compound 1-1-116 can be prepared based on Preparation Examples 1 to 22 by modifying the bonded substituent.
如同與製備例中的相同方式製備出化合物，且其合成之確認結果示於表1及表2。表1係關於1 H NMR (CDCl3 , 200 Mz)的測量值，且表2係關於場退吸質譜儀 (FD-MS) 的測量值。The compound was prepared in the same manner as in the Preparation Example, and the results of the synthesis thereof are shown in Table 1 and Table 2. Table 1 is a measurement of 1 H NMR (CDCl 3 , 200 Mz), and Table 2 is a measurement of a field desorption mass spectrometer (FD-MS).
＜ 製備例 23＞ 製備化合物 2-1-18 < Preparation Example 23> Preparation of Compound 2-1-18
製備化合物Preparation of compounds 11-111-1
在一單頸圓底燒瓶中，取乙基-o -磺醯基乙醯羥胺(13.26 g, 46.47 mmol) 溶於12 mL之1,4-二惡烷，然後將此反應溶液維持在0°C。緩慢逐滴添加過氯酸(70%, 5.40 mL) ，於維持該溫度下作用2分鐘，然後將此反應混合物攪拌5分鐘。待混合溶液中的反應終止，利用 H2 O/醚進行萃取並以MgSO4 乾燥，然後進行過濾。在減壓下蒸餾後得到固體化合物11-1 (9.33 g, 93%)。 In a single-necked round bottom flask, ethyl- o -sulfonylacetamide (13.26 g, 46.47 mmol) was dissolved in 12 mL of 1,4-dioxane, and the reaction solution was maintained at 0 °. C. Perchloric acid (70%, 5.40 mL) was slowly added dropwise, maintained at this temperature for 2 minutes, and then the reaction mixture was stirred for 5 minutes. The reaction in the mixed solution was terminated, extracted with H 2 O/ether and dried over MgSO 4 and then filtered. The solid compound 11-1 (9.33 g, 93%) was obtained after distillation under reduced pressure.
製備化合物Preparation of compounds 12-112-1
在一雙頸圓底燒瓶中，取四溴甲烷(42.2 g, 127.25 mol) 及三苯基膦(68.4 g, 260.88 mol) 於氮氣環境下完全溶解於500 mL之二氯甲烷 ，然後將此反應溶液維持在0°C下攪拌30分鐘。之後，緩慢逐滴添加異喹啉-3-甲醛 (10 g, 63.63 mmol) 作用10分鐘，然後將此反應溶液維持在0°C下攪拌1小時。待反應終止，利用二氯甲烷/H2 O萃取該反應混合物並以MgSO4 乾燥，然後進行過濾。將該混合物濃縮，然後使用己烷並過濾，以製造出固體產物 (19.5 g, 62.3 mmol, 98%)將該固體產物完全溶於200 mL之四氫呋喃，接著在溫度維持於-78°C下緩慢添加KOtBu (118 g, 1.06 mol) 。之後，添加100 ML鹵水(brine)，將該反應混合物冷卻至室溫，待反應終止，利用***/H2 O萃取該反應混合物並以MgSO4 乾燥，然後進行過濾。將該混合物濃縮，然後使用己烷製造出一固體，將該固體過濾後得到乳白色固體化合物12-1 (14.3 g, 99%)。In a double neck round bottom flask, tetrabromomethane (42.2 g, 127.25 mol) and triphenylphosphine (68.4 g, 260.88 mol) were completely dissolved in 500 mL of dichloromethane under nitrogen, and then the reaction solution was taken. Stir at 0 ° C for 30 minutes. Thereafter, isoquinoline-3-carbaldehyde (10 g, 63.63 mmol) was slowly added dropwise for 10 minutes, and then the reaction solution was stirred at 0 ° C for 1 hour. After the reaction was terminated, the reaction mixture was extracted with dichloromethane / H 2 O and dried over MgSO 4 and then filtered. The mixture was concentrated, then hexanes was used and filtered to give a solid product (19.5 g, 62.3 mmol, 98%). The solid product was completely dissolved in 200 mL of tetrahydrofuran and then slowly maintained at -78 ° C. Add KOtBu (118 g, 1.06 mol). After that, 100 ML of brine was added, and the reaction mixture was cooled to room temperature. After the reaction was terminated, the mixture was extracted with diethyl ether/H 2 O and dried over MgSO 4 and then filtered. The mixture was concentrated, then a solid was obtained using hexane, and the solid was filtered to afford compound 12-1 (14.3 g, 99%).
製備化合物Preparation of compounds 12-212-2
在一單頸圓底燒瓶中，取化合物11-1 (10 g, 46.45 mmol) 完全溶解於50 mL二氯甲烷，然後將此反應溶液維持在0°C。取化合物12-1 (9.70 g, 41.81 mmol) 完全溶解於50 mL二氯甲烷，將該反應溶液緩慢逐滴添加至前述單頸圓底燒瓶中。將該混合物攪拌約10分鐘後，加入300 mL***，再將該反應混合物攪拌30分鐘。製造出白色固體，經過濾、以乙酸乙酯/甲醇再結晶後，得到白色固體化合物12-2 (16.4 g, 92%)。In a one-necked round bottom flask, Compound 11-1 (10 g, 46.45 mmol) was dissolved in 50 mL of dichloromethane, and then the reaction solution was maintained at 0 °C. Compound 12-1 (9.70 g, 41.81 mmol) was completely dissolved in 50 mL of dichloromethane, and the reaction solution was slowly added dropwise to the above-mentioned single-necked round bottom flask. After the mixture was stirred for about 10 minutes, 300 mL of diethyl ether was added and the reaction mixture was stirred for 30 minutes. The title compound was obtained as a white solid.
製備化合物Preparation of compounds 12-312-3
取6 g之K2 CO3 置入一單頸圓底燒瓶中，將化合物12-2 (10 g, 26.09 mmol) 溶於10 mL二甲基甲醯胺後，緩慢逐滴添加至該單頸圓底燒瓶中。於室溫下攪拌該混合物約6小時，然後利用二氯甲烷/H2 O萃取、以硫酸鎂乾燥、然後過濾。將產物濃縮後，利用管柱層析分離(SiO2 , 二氯甲烷)，以得到白色固體化合物12-3 (6.1 g, 95%)。 6 g of K 2 CO 3 was placed in a single-necked round bottom flask, and compound 12-2 (10 g, 26.09 mmol) was dissolved in 10 mL of dimethylformamide and slowly added dropwise to the single neck. In a round bottom flask. The mixture was stirred at room temperature for about 6 hours, then extracted with dichloromethane / H 2 O, dried over magnesium sulfate and then filtered. After concentrating the product, it was purified by column chromatography (SiO 2 , methylene chloride) to afford white solid compound 122-3 (6.1 g, 95%).
製備化合物Preparation of compounds 2-1-182-1-18
在一單頸圓底燒瓶中，取化合物12-3 (10 g, 40.47 mmol) 於氮氣環境下溶於無水四氫呋喃(THF) (50 ml) ，然後將反應溶液冷卻至-78°C。取正丁基鋰 (2.5 M溶於己烷) (21 ml, 52.61 mmol) 緩慢逐滴添加至該反應溶液，然後將該反應混合物攪拌1小時。取氯二苯基膦(11.61 ml, 52.61 mol) 逐滴添加至該溶液，然後將該反應混合物於室溫下攪拌12小時。將該反應混合物以二氯甲烷/H2 O萃取，然後於減壓下蒸餾。將該反應混合物溶於二氯甲烷(250 ml) ，然後將該反應溶液連同20 ml之30% H2 O2 水溶液於室溫下攪拌12小時。將該反應混合物以二氯甲烷/H2 O萃取，經濃縮後之混合物利用管柱層析分離 (SiO2 , 二氯甲烷: 甲醇 = 25 : 1)，以得到黃色固體化合物2-1-18 (5.52 g, 37%)。In a one-neck round bottom flask, compound 12-3 (10 g, 40.47 mmol) was dissolved in anhydrous tetrahydrofuran (THF) (50 ml) under nitrogen atmosphere, and then the reaction solution was cooled to -78 °C. N-Butyllithium (2.5 M in hexane) (21 ml, 52.61 mmol) was slowly added dropwise to the reaction solution, and then the mixture was stirred for 1 hour. Chlorodiphenylphosphine (11.61 ml, 52.61 mol) was added dropwise to the solution, and the reaction mixture was stirred at room temperature for 12 hours. The reaction mixture was extracted with dichloromethane / H 2 O and then distilled under reduced pressure. The reaction mixture was dissolved in dichloromethane (250 ml), then the reaction solution was stirred together with 20 ml of 30% aqueous H 2 O 2 at room temperature for 12 hours. The reaction mixture was extracted with dichloromethane/H 2 O, and the mixture was concentrated and purified by column chromatography (SiO 2 , methylene chloride : methanol = 25 : 1 ) (5.52 g, 37%).
＜ 製備例 24＞ 製備化合物 2-1-86 < Preparation Example 24> Preparation of Compound 2-1-86
製備化合物Preparation of compounds D-1D-1
在一單頸圓底燒瓶中，混合(9,9-二甲基-9H-芴-2-基)硼酸(25.9 g, 0.108 mol) 、1-溴-2-硝基苯(20 g, 0.099 mol)、四(三苯基膦) 鈀(5.7 g, 4.95 mmol)、碳酸鉀(27.3 g, 0.198 mol)、及四氫呋喃(250 ml)/H2 O (50 ml)得到一混合物，將其回流並攪拌24小時。移除水相層，將該有機層以MgSO4 乾燥。將該有機層濃縮後以管柱層析(SiO2 , 己烷 : 二氯甲烷 = 2 : 1)分離，得到黃色固體化合物D-1 (21 g, 61%).In a single neck round bottom flask, mix (9,9-dimethyl-9H-indol-2-yl)boronic acid (25.9 g, 0.108 mol), 1-bromo-2-nitrobenzene (20 g, 0.099) Mol), tetrakis(triphenylphosphine)palladium (5.7 g, 4.95 mmol), potassium carbonate (27.3 g, 0.198 mol), and tetrahydrofuran (250 ml) / H 2 O (50 ml) to give a mixture and reflux Stir for 24 hours. Removing the aqueous layer, the organic layer was dried MgSO 4. The organic layer was concentrated and purified by column chromatography (SiO 2 , hexane: methylene chloride = 2 : 1) to afford compound D-1 (21 g, 61%).
製備化合物Preparation of compounds D-2D-2
在一單頸圓底燒瓶中，混合化合物D-1 (20 g, 0.0634 mmol), 、三苯基膦(49.8 g, 0.190 mol)、及鄰二氯苯 (300 ml) 得到一混合物，將其回流並於氮氣環境下攪拌18小時。在減壓下蒸餾移除o-DCB，以管柱層析(SiO2 , 己烷 : 二氯甲烷 = 3: 1)分離，得到白色固體化合物D-2 (6.6 g, 36%)。In a one-neck round bottom flask, compound D-1 (20 g, 0.0634 mmol), triphenylphosphine (49.8 g, 0.190 mol), and o-dichlorobenzene (300 ml) were mixed to obtain a mixture. It was refluxed and stirred under a nitrogen atmosphere for 18 hours. O-DCB removed by distillation under reduced pressure, purified by column chromatography (SiO 2, hexane: dichloromethane = 3: 1) to give D-2 (6.6 g, 36 %) as a white solid compound.
製備化合物Preparation of compounds 2-1-862-1-86
在一單頸圓底燒瓶中，混合化合物12-3 (6.0 g, 24.28 mmol)、化合物D-2 (6.19 g, 21.85 mmol)、Cu (0.15 g, 2.43 mmol) 、18-冠-6-醚(0.64 g, 2.43 mmol) 、 碳酸鉀(10.1 g, 72.84 mmol) 、及鄰二氯苯(80 ml) 得到一混合物，將其回流並於氮氣環境下攪拌24小時。在減壓下蒸餾移除o-DCB，以管柱層析(SiO2 , 己烷 : 二氯甲烷 = 4: 1)分離，得到白色固體化合物2-1-86 (6.4 g, 64%).In a single neck round bottom flask, compound 12-3 (6.0 g, 24.28 mmol), compound D-2 (6.19 g, 21.85 mmol), Cu (0.15 g, 2.43 mmol), 18-crown-6-ether (0.64 g, 2.43 mmol), potassium carbonate (10.1 g, 72.84 mmol), and o-dichlorobenzene (80 ml) obtained a mixture which was refluxed and stirred under nitrogen for 24 hours. Distilled under reduced pressure to remove o-DCB, by column chromatography (SiO 2, hexane: dichloromethane = 4: 1) to obtain a white solid compound 2-1-86 (6.4 g, 64%) .
＜ 製備例 25＞ 製備化合物 2-1-37 < Preparation Example 25> Preparation of Compound 2-1-37
製備化合物Preparation of compounds 13-113-1
在一雙頸圓底燒瓶中，混合化合物12-3 (6.0 g, 24.28 mmol) 、雙（頻哪醇）二硼(7.4 g, 29.14 mmol) 、醋酸鉀(4.77 g, 48.56 mmol) 、 PdCl2 (dppf) (0.8 g, 1.21 mmol) 、及1,4-二惡烷(120 ml) 得到一混合溶液，將其回流並於氮氣環境下攪拌3小時。 將該反應混合物冷卻至室溫，以二氯甲烷/H2 O萃取並以硫酸鎂乾燥，然後過濾。混合物經濃縮後，使用己烷以製造一固體，過濾該固體後得到乳白色固體化合物13-1 (6.2 g, 88%)。In a double necked round bottom flask, compound 12-3 (6.0 g, 24.28 mmol), bis(pinacol) diboron (7.4 g, 29.14 mmol), potassium acetate (4.77 g, 48.56 mmol), PdCl 2 (dppf) (0.8 g, 1.21 mmol) and 1,4-dioxane (120 ml) gave a mixed solution, which was refluxed and stirred under nitrogen for 3 hours. The reaction mixture was cooled to room temperature, extracted with dichloromethane / H 2 O and dried over magnesium sulfate. After the mixture was concentrated, hexane was used to give a solid, and the solid was filtered to afford compound 13-1 (6.2 g, 88%).
製備化合物Preparation of compounds 2-1-372-1-37
在一雙頸圓底燒瓶中，混合化合物13-1 (6.0 g, 20.40 mmol) 、2-溴-4,6-二苯基嘧啶(6.98 g, 22.44 mmol) 、醋酸鉀(5.64 g, 40.8 mmol) 、四(三苯基膦) 鈀(1.18 g, 1.02 mmol) 及甲苯/乙醇(EtOH)/H2 O (60 ml/12 ml/12 ml) 得到一混合溶液，將其回流並於氮氣環境下攪拌12小時。將反應混合物中的溶劑濾出，依序以100 ml甲苯、150 ml己烷、及150 ml甲醇清洗，以得到白色固體化合物2-1-37 (7.1 g, 88%)。In a double necked round bottom flask, compound 13-1 (6.0 g, 20.40 mmol), 2-bromo-4,6-diphenylpyrimidine (6.98 g, 22.44 mmol), potassium acetate (5.64 g, 40.8 mmol) , tetrakis(triphenylphosphine)palladium (1.18 g, 1.02 mmol) and toluene/ethanol (EtOH)/H 2 O (60 ml/12 ml/12 ml) to obtain a mixed solution, which is refluxed and placed in a nitrogen atmosphere. Stir under 12 hours. The solvent in the reaction mixture was filtered, washed with EtOAc EtOAcjjjjjj
＜ 製備例 26＞ 製備化合物 2-1-63 < Preparation Example 26> Preparation of Compound 2-1-63
製備化合物Preparation of compounds 13-213-2
在一單頸圓底燒瓶中，混合化合物13-1 (6.0 g, 20.40 mmol) 、1-碘-4-溴苯(6.35 g, 22.44 mmol) 、碳酸鉀(5.64 g, 40.8 mmol) 、Pd(PPh3 )4 (1.18 g, 1.02 mmol) 、及甲苯/乙醇/H2 O (60 ml/12 ml/12 ml) 得到一混合溶液，將其回流並攪拌6小時。將反應混合物中的溶劑濾出，依序以100 ml甲苯、150 ml己烷、及150 ml甲醇清洗，以得到白色固體化合物13-2 (3.6 g, 55%)。In a single neck round bottom flask, compound 13-1 (6.0 g, 20.40 mmol), 1-iodo-4-bromobenzene (6.35 g, 22.44 mmol), potassium carbonate (5.64 g, 40.8 mmol), Pd ( PPh 3 ) 4 (1.18 g, 1.02 mmol), and toluene/ethanol/H 2 O (60 ml / 12 ml / 12 ml) gave a mixed solution which was refluxed and stirred for 6 hours. The solvent in the reaction mixture was filtered, washed sequentially with 100 ml of toluene, 150 ml of hexane, and 150 ml of methanol to give white solid compound 13-2 (3.6 g, 55%).
製備化合物Preparation of compounds 2-1-632-1-63
在一雙頸圓底燒瓶中，混合化合物13-2 (4.0 g, 12.38 mmol) 、[1,1':3',1''-三聯苯基]-5'-基-硼酸(3.73 g, 13.61 mmol)、碳酸鉀(3.42 g, 24.76 mmol) 、四(三苯基膦) 鈀(0.72 g, 0.62 mmol) 、及甲苯/乙醇/H2 O (40 ml/8 ml/8 ml) 得到一混合溶液，將其回流並於氮氣環境下攪拌12小時。將反應混合物中的溶劑濾出，依序以50 ml甲苯、80 ml己烷、及80 ml甲醇清洗，以得到白色固體化合物2-1-63 (4.5 g, 77%)。In a double necked round bottom flask, compound 13-2 (4.0 g, 12.38 mmol), [1,1':3',1''-triphenyl]-5'-yl-boronic acid (3.73 g, 13.61 mmol), potassium carbonate (3.42 g, 24.76 mmol), tetrakis(triphenylphosphine)palladium (0.72 g, 0.62 mmol), and toluene/ethanol/H 2 O (40 ml/8 ml/8 ml) The solution was mixed, refluxed and stirred under nitrogen for 12 hours. The solvent in the reaction mixture was filtered, washed with 50 ml of toluene, 80 ml of hexane, and 80 ml of methanol to give white solid compound 2-2-1 (4.5 g, 77%).
化合物13-2具有一型式，其中在式3的核心結構中，於R1位置溴甲苯基被取代。在製備例26中，化合物13-2的溴(Br)經由三聯苯基取代，以製備出化合物2-1-63。Compound 13-2 has a type in which a bromotolyl group at the R1 position is substituted in the core structure of Formula 3. In Preparation Example 26, bromine (Br) of Compound 13-2 was substituted with a terphenyl group to prepare Compounds 2-1-63.
例如，本技術領域中具有通常知識者可以調整製備例26，導入三聯苯基以外的取代基。當使用化合物13-2取代化合物12-3用以製備化合物2-1-18時，得到之化合物結構中，導入經二苯基磷取代之苯基(化合物2-1-196)。For example, those skilled in the art can adjust Preparation Example 26 to introduce a substituent other than a terphenyl group. When Compound 13-2 is used instead of Compound 12-3 to prepare Compound 2-1-18, a phenyl group substituted with diphenylphosphine (Compounds 2-1-196) is introduced into the structure of the obtained compound.
換言之，能夠製備出包含磷系取代基的化合物，其在式3之核心結構中具有亞芳基聯結基團。例如，化合物2-1-74及化合物2-1-139為包含磷系取代基的化合物，具有亞芳基聯結基團。In other words, a compound containing a phosphorus-based substituent having an arylene bond group in the core structure of Formula 3 can be prepared. For example, the compounds 2-1-1-74 and the compounds 2-1-1-139 are compounds containing a phosphorus-based substituent and have an arylene-bonding group.
此外，藉由利用製備例23之化合物12-3取代製備例26之化合物13-2，如三聯苯基之取代基可以直接導入式3之核心結構中。Further, by substituting the compound 13-3 of Preparation Example 23 for the compound 13-2 of Preparation Example 26, a substituent such as a terphenyl group can be directly introduced into the core structure of Formula 3.
＜ 製備例 27＞ 製備化合物 2-1-180 < Preparation Example 27> Preparation of Compound 2-1-180
在一雙頸圓底燒瓶中，混合化合物13-2 (5.0 g, 15.47 mmol) 、3,5-二(9H-咔唑基-9-基)苯基)硼酸(7.7 g, 17.02 mmol) 、K2 CO3 (4.28 g, 30.94 mmol) 、四(三苯基膦)鈀(0.89 g, 0.77 mmol) 、及甲苯/乙醇/H2 O (100 ml/20 ml/20 ml) 得到一混合溶液，將其回流並於氮氣環境下攪拌12小時。 將該反應混合物冷卻至室溫，利用二氯甲烷/H2 O萃取並以硫酸鎂乾燥，然後過濾。該產物經濃縮後，接著用管柱層析(SiO2 , 己烷: 二氯甲烷 = 2 : 1)分離，以得到白色固體化合物2-1-180 (7.85 g, 78%)。In a double necked round bottom flask, compound 13-2 (5.0 g, 15.47 mmol), 3,5-bis(9H-carbazolyl-9-yl)phenyl)boronic acid (7.7 g, 17.02 mmol), a mixed solution of K 2 CO 3 (4.28 g, 30.94 mmol), tetrakis(triphenylphosphine)palladium (0.89 g, 0.77 mmol), and toluene/ethanol/H 2 O (100 ml/20 ml/20 ml) It was refluxed and stirred under a nitrogen atmosphere for 12 hours. The reaction mixture was cooled to room temperature, extracted with dichloromethane / H 2 O and dried over magnesium sulfate. After the product was concentrated, followed by column chromatographic separation (of SiO 2, hexanes: 1: methylene chloride = 2), to give a white solid compound 2-1-180 (7.85 g, 78%) .
＜ 製備例 28＞ 製備化合物 2-1-109 < Preparation Example 28> Preparation of Compound 2-1-109
製備化合物Preparation of compounds E-1E-1
在一雙頸圓底燒瓶中，混合2-溴-4,6-二苯基-1,3,5-三嗪(10.0 g, 32.03 mmol) 、雙（頻哪醇）二硼(9.76 g, 38.44 mol) 、醋酸鉀(6.29 g, 64.06 mmol) 、PdCl2 dppf (dppf: 1,1'-雙(二苯基磷) 二茂鐵) (1.17 g, 1.60 mmol) 及1,4-二惡烷得到一混合溶液，將其回流並於氮氣環境下攪拌3小時。 將該反應混合物冷卻至室溫，以二氯甲烷/H2 O萃取並以硫酸鎂乾燥，然後過濾。混合物經濃縮後，使用己烷以製造一固體，過濾該固體後得到乳白色固體化合物E-1 (19.67 g, 83%)。In a double neck round bottom flask, 2-bromo-4,6-diphenyl-1,3,5-triazine (10.0 g, 32.03 mmol), bis(pinacol) diboron (9.76 g, 38.44 mol), potassium acetate (6.29 g, 64.06 mmol), PdCl 2 dppf (dppf: 1,1'-bis(diphenylphosphino)ferrocene) (1.17 g, 1.60 mmol) and 1,4-dioxin A mixed solution of the alkane was obtained, which was refluxed and stirred under nitrogen for 3 hr. The reaction mixture was cooled to room temperature, extracted with dichloromethane / H 2 O and dried over magnesium sulfate. After the mixture was concentrated, hexane was used to give a solid, and the solid was filtered to give the white solid compound E-1 (19.67 g, 83%).
製造化合物Manufacturing compound 14-114-1
在一單頸圓底燒瓶中，混合化合物13-1 (8.0 g, 27.20 mmol) 、1-碘-3-溴苯(8.46 g, 29.92 mmol) 、碳酸鉀(7.52 g, 54.5 mmol) 、Pd(PPh3 )4 (1.57 g, 1.36 mmol) 、及甲苯/乙醇/H2 O (80 ml/16 ml/16 ml) 得到一混合溶液，將其回流並攪拌6小時。將反應混合物中的溶劑濾出，依序以100 ml甲苯、150 ml己烷、及150 ml甲醇清洗，以得到白色固體化合物14-1 (6.1 g, 69%)。In a single neck round bottom flask, compound 13-1 (8.0 g, 27.20 mmol), 1-iodo-3-bromobenzene (8.46 g, 29.92 mmol), potassium carbonate (7.52 g, 54.5 mmol), Pd ( PPh 3 ) 4 (1.57 g, 1.36 mmol), and toluene/ethanol/H 2 O (80 ml/16 ml/16 ml) gave a mixed solution which was refluxed and stirred for 6 hours. The solvent in the reaction mixture was filtered, washed with 100 ml of toluene, 150 ml of hexane, and 150 ml of methanol to give white solid compound 14-1 (6.1 g, 69%).
製備化合物Preparation of compounds 2-1-1092-1-109
在一雙頸圓底燒瓶中，混合化合物14-1 (5.0 g, 15.47 mmol) 、2,4-二苯基-6-(4,4,5,5-四甲基-1,3,2-二氧硼烷-2-基)-1,3,5-三嗪(6.67 g, 18.56 mmol)、碳酸鉀 (4.28 g, 30.94 mmol)、四(三苯基膦)鈀(0.89 g, 0.77 mol) 、及甲苯/乙醇/H2 O (100 ml/20 ml/20 ml) 得到一混合溶液，將其回流並於氮氣環境下攪拌12小時。 將該反應混合物冷卻至室溫，利用二氯甲烷/H2 O萃取並以硫酸鎂乾燥，然後過濾。該產物經濃縮後，接著用管柱層析(SiO2 , 己烷: 二氯甲烷 = 4 : 1)分離，以得到白色固體化合物2-1-109 (6.0 g, 82%)。In a double necked round bottom flask, compound 14-1 (5.0 g, 15.47 mmol), 2,4-diphenyl-6-(4,4,5,5-tetramethyl-1,3,2 -dioxaborolan-2-yl)-1,3,5-triazine (6.67 g, 18.56 mmol), potassium carbonate (4.28 g, 30.94 mmol), tetrakis(triphenylphosphine)palladium (0.89 g, 0.77 Mol), and toluene/ethanol/H 2 O (100 ml/20 ml/20 ml) gave a mixed solution which was refluxed and stirred under nitrogen for 12 hours. The reaction mixture was cooled to room temperature, extracted with dichloromethane / H 2 O and dried over magnesium sulfate. After the product was concentrated, followed by column chromatography (SiO 2, hexanes: 1: methylene chloride = 4), to give a white solid compound 2-1-109 (6.0 g, 82%) .
＜ 製備例 29＞ 製備化合物 2-1-120 < Preparation Example 29> Preparation of Compound 2-1-120
製備化合物 F-1 Preparation of compound F-1
在一單頸圓底燒瓶中，混合1,2-二環己酮(30.0 g, 0.374 mol)、苯肼鹽酸(phenylhydrazine hydrochloride)(77.37 g, 0.749 mol)、及乙醇(1,000 ml)，得到一混合物，在氮氣環境下緩慢逐滴添加硫酸(1.4 mL, 0.0374 mol)，然後將該反應混合物於60°C下攪拌4小時。將該溶液冷卻至室溫，經過濾後得到黃棕色固體(69 g, 93%). 在一單頸圓底燒瓶中，混合該固體(68.9 g, 0.25 mol)及醋酸(700 ml) 得到一混合物，添加三氟乙酸(46.5 mL, 0.6 mol)，且該反應混合物於100°C下攪拌12小時。該溶液冷卻至室溫後，以醋酸和己烷清洗，經過濾後得到乳白色固體F-1 (27.3 g, 42%)。In a single neck round bottom flask, 1,2-dicyclohexanone (30.0 g, 0.374 mol), phenylhydrazine hydrochloride (77.37 g, 0.749 mol), and ethanol (1,000 ml) were mixed to obtain a The mixture was slowly added dropwise with sulfuric acid (1.4 mL, 0.0374 mol) under a nitrogen atmosphere, and then the mixture was stirred at 60 ° C for 4 hours. The solution was cooled to room temperature and filtered to give a brown solid (yield: 69 g, 93%). In a single-necked round bottom flask, the solid (68.9 g, 0.25 mol) and acetic acid (700 ml) were mixed. The mixture was added with trifluoroacetic acid (46.5 mL, 0.6 mol), and the mixture was stirred at 100 ° C for 12 hr. After the solution was cooled to room temperature, it was washed with ethyl acetate and hexane, and filtered to give a white solid solid F-1 (27.3 g, 42%).
製備化合物Preparation of compounds F-2F-2
在一雙頸圓底燒瓶中，混合化合物F-1 (2.1 g, 0.0082 mol) 、碘苯(2.5 g, 0.013 mol)、Cu (0.312 g, 0.0049)、18-冠-6-醚(0.433 g, 0.0016 mol)、碳酸鉀(3.397 g, 0.0246 mol)、及鄰二氯苯(20 ml) 得到一混合物，將其回流並於氮氣環境下攪拌12小時。將該反應混合物冷卻至室溫，以二氯甲烷/H2 O萃取並濃縮，以管柱層析(SiO2 , 己烷 : 乙酸乙酯 =10: 1)分離，得到白色固體化合物F-2 (1.76 g, 64%)。In a double necked round bottom flask, compound F-1 (2.1 g, 0.0082 mol), iodobenzene (2.5 g, 0.013 mol), Cu (0.312 g, 0.0049), 18-crown-6-ether (0.433 g) A mixture of 0.0016 mol), potassium carbonate (3.397 g, 0.0246 mol) and o-dichlorobenzene (20 ml) was refluxed and stirred under nitrogen for 12 hours. The reaction mixture was cooled to room temperature, dichloromethane / H 2 O and extracted and concentrated, purified by column chromatography (SiO 2, hexane: ethyl acetate = 10: 1) to obtain a white solid compound F-2 (1.76 g, 64%).
製備化合物Preparation of compounds 2-1-1202-1-120
在一單頸圓底燒瓶中，混合化合物14-1 (6.0 g, 24.28 mmol) 、化合物F-2 (9.69 g, 29.14 mmol)、Cu (0.15 g, 2.43 mmol) 、18-冠-6-醚 (0.64 g, 2.43 mmol) 、碳酸鉀(6.71 g, 48.56 mmol) 、及鄰二氯苯(60 ml) 得到一混合物，將其回流並於氮氣環境下攪拌24小時。在減壓下蒸餾移除鄰二氯苯，然後以管柱層析(SiO2 , 己烷 : 二氯甲烷 =3: 1)分離，得到白色固體化合物2-1-120 (6.7 g, 48%)。In a single neck round bottom flask, compound 14-1 (6.0 g, 24.28 mmol), compound F-2 (9.69 g, 29.14 mmol), Cu (0.15 g, 2.43 mmol), 18-crown-6-ether A mixture of (0.64 g, 2.43 mmol), potassium carbonate (6.71 g, 48.56 mmol) and o-dichlorobenzene (60 ml) was refluxed and stirred under nitrogen for 24 hours. The o-dichlorobenzene was removed by distillation under reduced pressure, and then purified by column chromatography (SiO 2 , hexane : methylene chloride = 3: 1) to give white solid compound 2-1-2 ( 6.7 g, 48% ).
＜ 製備例 30＞ 製備化合物 2-1-154 < Preparation Example 30> Preparation of Compound 2-1-154
製備化合物Preparation of compounds 15-115-1
在一單頸圓底燒瓶中，混合化合物12-3 (6.0 g, 24.28 mmol) 、苯基硼酸(3.55 g, 29.14 mmol)、碳酸鉀(6.71 g, 48.56 mmol)、四(三苯基膦) 鈀(1.40 g, 1.21 mmol)、及甲苯/乙醇/H2 O (60 ml/12 ml/12 ml) 得到一混合物，將其回流並攪拌6小時。將反應混合物中的溶劑濾出，依序以50 ml甲苯、80 ml己烷、及80 ml甲醇清洗，以得到白色固體化合物15-1 (5.8 g, 98%)。In a single neck round bottom flask, compound 12-3 (6.0 g, 24.28 mmol), phenylboronic acid (3.55 g, 29.14 mmol), potassium carbonate (6.71 g, 48.56 mmol), tetrakis(triphenylphosphine) Palladium (1.40 g, 1.21 mmol), and toluene/ethanol/H 2 O (60 ml / 12 ml / 12 ml) gave a mixture which was refluxed and stirred for 6 hours. The solvent in the reaction mixture was filtered, washed with 50 ml of toluene, 80 ml of hexane, and 80 ml of methanol to give white solid compound 15-1 (5.8 g, 98%).
製備化合物Preparation of compounds 15-215-2
取100 mL之CHCl3 及br2 (2.1 mL, 40.94 mmol)置入一單頸圓底燒瓶中，將該反應混合物攪拌10分鐘，然後使溫度維持在0°C。取化合物15-1 (5 g, 20.47 mmol)溶於50 mL氯仿中，然後緩慢逐滴添加至該單頸圓底燒瓶中。約1小時後反應終止，利用二氯甲烷/H2 O萃取該產物並濃縮，然後以少量EA和己烷清洗，得到固體化合物15-2 (6.4 g, 97%)。100 mL of CHCl 3 and br 2 (2.1 mL, 40.94 mmol) were placed in a one-neck round bottom flask, and the reaction mixture was stirred for 10 minutes, and then the temperature was maintained at 0 °C. Compound 15-1 (5 g, 20.47 mmol) was dissolved in 50 mL of chloroform and then slowly added dropwise to the one-neck round bottom flask. After about 1 hour, the reaction was quenched, the product was extracted with dichloromethane/H 2 O and concentrated, then washed with a small amount of EA and hexane to give solid compound 15-2 (6.4 g, 97%).
製備化合物Preparation of compounds 2-1-1542-1-154
在一單頸圓底燒瓶中，混合化合物15-2 (6.0 g, 18.56 mmol) 、 2,4-二苯基-6-(4,4,5,5-四甲基-1,3,2-二氧硼烷-2-基)-1,3,5-三嗪(8.0 g, 22.28 mmol)、碳酸鉀(5.13 g, 37.12 mmol) 、四(三苯基膦)鈀(1.07 g, 0.93 mmol)、及甲苯/乙醇/H2 O (60 ml/12 ml/12 ml) 得到一混合溶液，將其回流並攪拌12小時。 將該反應混合物冷卻至室溫，利用二氯甲烷/H2 O萃取並濃縮，接著用管柱層析(SiO2 , 己烷: 二氯甲烷 = 3 : 1)分離，以得到白色固體化合物2-1-154 (7.76 g, 88%)。In a single neck round bottom flask, compound 15-2 (6.0 g, 18.56 mmol), 2,4-diphenyl-6-(4,4,5,5-tetramethyl-1,3,2 -dioxaborolan-2-yl)-1,3,5-triazine (8.0 g, 22.28 mmol), potassium carbonate (5.13 g, 37.12 mmol), tetrakis(triphenylphosphine)palladium (1.07 g, 0.93 Methyl), and toluene/ethanol/H 2 O (60 ml / 12 ml / 12 ml) gave a mixed solution which was refluxed and stirred for 12 hours. The reaction mixture was cooled to room temperature, extracted with dichloromethane/H 2 O and concentrated, and then purified by column chromatography (SiO 2 , hexane : methylene chloride = 3 : 1 ) to afford white solid compound 2 -1-154 (7.76 g, 88%).
＜ 製備例 31＞ 製備化合物 2-1-186 < Preparation Example 31> Preparation of Compound 2-1-186
在一單頸圓底燒瓶中，混合化合物13-1 (6.0 g, 20.4 mmol)、化合物13-2 (7.9 g, 24.48 mmol)、碳酸鉀 (8.46 g, 61.2 mmol) 、四(三苯基膦)鈀(1.18 g, 1.02 mmol) 、及甲苯/乙醇/H2 O (60 ml/12 ml/12 ml) 得到一混合溶液，將其回流並攪拌12小時。 將該反應混合物冷卻至室溫，利用二氯甲烷/H2 O萃取並濃縮，接著用管柱層析(SiO2 , 己烷: 二氯甲烷 = 4 : 1)分離，以得到白色固體化合物2-1-186 (5.49 g, 72%)。In a single neck round bottom flask, compound 13-1 (6.0 g, 20.4 mmol), compound 13-2 (7.9 g, 24.48 mmol), potassium carbonate (8.46 g, 61.2 mmol), tetrakis(triphenylphosphine) Palladium (1.18 g, 1.02 mmol), and toluene/ethanol/H 2 O (60 ml / 12 ml / 12 ml) gave a mixed solution which was refluxed and stirred for 12 hours. The reaction mixture was cooled to room temperature, extracted with dichloromethane/H 2 O and concentrated, and then purified by column chromatography (SiO 2 , hexane : methylene chloride = 4 : 1 ) to afford white solid compound 2 -1-186 (5.49 g, 72%).
＜ 製備例 32＞ 製備化合物 2-1-190 < Preparation Example 32> Preparation of Compound 2-1-190
在一單頸圓底燒瓶中，取化合物13-2 (10 g, 30.94 mmol)完全溶於 200 mL四氫呋喃，然後維持溫度於-78°C時緩慢逐滴添加正丁基鋰(6.6 mL, 32.04 mmol)。將反應混合物攪拌約30分鐘，然後緩慢逐滴添加氯三苯基矽烷(10.03 g, 34.03 mmol)，約1小時後反應終止，利用二氯甲烷/H2 O萃取並濃縮產物，接著用管柱層析(SiO2 , 己烷: 二氯甲烷 = 4 : 1)分離，以得到白色固體化合物2-1-190 (5.76 g, 37%)。In a single neck round bottom flask, compound 13-2 (10 g, 30.94 mmol) was dissolved in 200 mL of tetrahydrofuran, and then n-butyllithium (6.6 mL, 32.04) was slowly added dropwise while maintaining the temperature at -78 °C. Mm). The reaction mixture was stirred for about 30 minutes, then chlorotriphenylnonane (10.03 g, 34.03 mmol) was slowly added dropwise, the reaction was quenched after about 1 hour, and the product was extracted with dichloromethane/H 2 O and then concentrated. Chromatography (SiO 2 , hexane : methylene chloride = 4 : 1)
＜ 製備例 33＞ 製備化合物 2-1-192 < Preparation Example 33> Preparation of Compound 2-1-192
在一單頸圓底燒瓶中，混合化合物13-1 (6.0 g, 20.4 mmol) 、2,6-二溴吡啶(5.8 g, 24.48 mmol)、碳酸鉀(8.46 g, 61.2 mmol) 、四(三苯基膦)鈀(1.18 g, 1.02 mmol), and 、及甲苯/乙醇/H2 O (60 ml/12 ml/12 ml) 得到一混合溶液，將其回流並攪拌6小時。將該反應混合物冷卻至室溫，利用二氯甲烷/H2 O萃取並濃縮，接著用管柱層析(SiO2 , 己烷: 二氯甲烷 =2 : 1)分離，以得到白色固體化合物2-1-192 (5.58 g, 66%)。In a single neck round bottom flask, compound 13-1 (6.0 g, 20.4 mmol), 2,6-dibromopyridine (5.8 g, 24.48 mmol), potassium carbonate (8.46 g, 61.2 mmol), four (three) Phenylphosphine)palladium (1.18 g, 1.02 mmol), and, and toluene/ethanol/H 2 O (60 ml / 12 ml / 12 ml) gave a mixed solution which was refluxed and stirred for 6 hours. The reaction mixture was cooled to room temperature, extracted with dichloromethane / H 2 O and concentrated, and then purified by column chromatography (SiO 2 , hexane : methylene chloride = 2 : 1 ) to give white solid compound 2 -1-192 (5.58 g, 66%).
＜ 製備例 34＞ 製備化合物 2-1-193 < Preparation Example 34> Preparation of Compound 2-1-193
在一單頸圓底燒瓶中，混合化合物12-3 (6.0 g, 24.28 mmol) 、二([1,1'-聯苯基]-4-基)胺) (7.0 g, 21.85 mmol)、Cu (0.15 g, 2.43 mmol)、18-冠-6-醚(0.64 g, 2.43 mmol)、碳酸鉀(10.1 g, 72.84 mmol) 、及鄰二氯苯(80 ml) 得到一混合物，將其回流並於氮氣環境下攪拌24小時。在減壓下蒸餾移除鄰二氯苯，以管柱層析(SiO2 , 己烷 : 二氯甲烷 = 5: 1)分離，得到白色固體化合物2-1-193 (6.57 g, 55%)。In a single neck round bottom flask, compound 12-3 (6.0 g, 24.28 mmol), bis([1,1'-biphenyl]-4-yl)amine (7.0 g, 21.85 mmol), Cu (0.15 g, 2.43 mmol), 18-crown-6-ether (0.64 g, 2.43 mmol), potassium carbonate (10.1 g, 72.84 mmol), and o-dichlorobenzene (80 ml). Stir under nitrogen for 24 hours. The o-dichlorobenzene was removed by distillation under reduced pressure, and purified by column chromatography (SiO 2 , hexane : methylene chloride = 5: 1) to afford white solid compound 2-1-193 (6.57 g, 55%) .
＜ 製備例 35＞ 製備化合物 2-1-200 < Preparation Example 35> Preparation of Compound 2-1-200
在一單頸圓底燒瓶中，混合o-DCB (80 ml)、化合物12-3 (6.0 g, 24.28 mmol)、試劑(8.2 g, 21.85 mmol)、Cu (0.15 g, 2.43 mmol)、18-冠-6-醚(0.79 g, 2.43 mmol)及K2 CO3 (10.1 g, 72.84 mmol) 得到一混合物，將其回流並於氮氣環境下攪拌12小時。在減壓下蒸餾移除o-DCB，以管柱層析(SiO2 , 己烷 : MC = 4: 1)分離，得到白色固體化合物2-1-200 (7.4 g, 56%).In a single neck round bottom flask, mix o-DCB (80 ml), compound 12-3 (6.0 g, 24.28 mmol), reagent (8.2 g, 21.85 mmol), Cu (0.15 g, 2.43 mmol), 18- crown-6 (0.79 g, 2.43 mmol) and K 2 CO 3 (10.1 g, 72.84 mmol) to give a mixture which was stirred and refluxed under nitrogen atmosphere for 12 hours. The o-DCB was removed by distillation under reduced pressure, and purified by column chromatography (SiO 2 , hexane : MC = 4: 1) to give white solid compound 2-1-200 (7.4 g, 56%).
＜ 製備例 36＞ 製備化合物 2-1-201 < Preparation Example 36> Preparation of Compound 2-1-201
利用與製備例35中製備化合物2-1-200的方法相同的方式，除了使用N-(9,9-二甲基-9H-芴-3-基) 二苯並[b,d]呋喃-4-胺取代方法中的N-(9,9-二甲基-9H-芴-3-基) 二苯並[b,d]呋喃-2-胺，製備出一產物(10.1 g, 77%)。The same procedure as in the preparation of the compound 2-1-200 in Preparation 35 except that N-(9,9-dimethyl-9H-indol-3-yl)dibenzo[b,d]furan- N-(9,9-dimethyl-9H-indol-3-yl)dibenzo[b,d]furan-2-amine in the 4-amine substitution method to prepare a product (10.1 g, 77%) ).
＜ 製備例 37＞ 製備化合物 2-1-202 < Preparation Example 37> Preparation of Compound 2-1-202
利用與製備例35中製備化合物2-1-200的方法相同的方式，除了使用N-([1,1’-二甲基]-3-基)-9,9-二甲基-9H-芴-4-胺取代方法中的N-(9,9-二甲基-9H-芴-3-基) 二苯並[b,d]呋喃-2-胺，製備出一產物(10.4 g, 49%)。The same procedure as in the preparation of the compound 2-1-200 in Preparation 35 except that N-([1,1'-dimethyl]-3-yl)-9,9-dimethyl-9H- was used. Preparation of a product (10.4 g, N-(9,9-dimethyl-9H-indol-3-yl)dibenzo[b,d]furan-2-amine in the oxime-4-amine substitution method 49%).
＜ 製備例 38＞ 製備化合物 2-1-203 < Preparation Example 38> Preparation of Compound 2-1-203
利用與製備例35中製備化合物2-1-200的方法相同的方式，除了使用N-(9,9’-螺二[芴]-3-基) 二苯並[b,d] 噻吩-2-胺取代方法中的N-(9,9-二甲基-9H-芴-3-基) 二苯並[b,d]呋喃-2-胺，製備出一產物(15.1 g, 55%)。The same procedure as in the preparation of the compound 2-1-200 in Preparation 35 except that N-(9,9'-spirobis[芴]-3-yl)dibenzo[b,d]thiophene-2 was used. - N-(9,9-dimethyl-9H-indol-3-yl)dibenzo[b,d]furan-2-amine in the amine substitution method to prepare a product (15.1 g, 55%) .
＜ 製備例 39＞ 製備化合物 2-1-204 < Preparation Example 39> Preparation of Compound 2-1-204
利用與製備例35中製備化合物2-1-200的方法相同的方式，，除了使用N-(9,9'-螺二[芴]-3-基)二苯並[b,d]呋喃-2-胺取代方法中的N-(9,9-二甲基-9H-芴-3-基) 二苯並[b,d]呋喃-2-胺，製備出一產物(11.8 g, 44%)。In the same manner as the method for preparing the compound 2-1-200 in Preparation 35, except that N-(9,9'-spirobis[indol-3-yl)dibenzo[b,d]furan- Preparation of a product (11.8 g, 44%) by N-(9,9-dimethyl-9H-indol-3-yl)dibenzo[b,d]furan-2-amine in a 2-amine substitution process ).
＜ 製備例 40＞ 製備化合物 2-1-206 < Preparation Example 40> Preparation of Compound 2-1-206
在一單頸圓底燒瓶中，混合o-DCB (80 ml) 、化合物12-3 (6.0 g, 24.28 mmol) 、試劑(8.9 g, 21.85 mmol)、Cu (0.15 g, 2.43 mmol) 、18-冠-6-醚(0.79 g, 2.43 mmol) 及K2 CO3 (10.1 g, 72.84 mmol) 得到一混合物，將其回流並於氮氣環境下攪拌12小時。在減壓下蒸餾移除o-DCB，以管柱層析(SiO2 , 己烷 : MC = 4: 1)分離，得到白色固體化合物2-1-206 (5.7 g, 41%)。In a single neck round bottom flask, mix o-DCB (80 ml), compound 12-3 (6.0 g, 24.28 mmol), reagent (8.9 g, 21.85 mmol), Cu (0.15 g, 2.43 mmol), 18- A mixture of crown-6-ether (0.79 g, 2.43 mmol) and K 2 CO 3 (10.1 g, 72.84 mmol) was obtained, which was refluxed and stirred under nitrogen for 12 hours. The o-DCB was removed by distillation under reduced pressure, and purified by column chromatography (SiO 2 , hexane : EtOAc = 4:1) to afford white solid compound 2-1-206 (5.7 g, 41%).
＜ 製備例 41＞ 製備化合物 2-1-207 < Preparation Example 41> Preparation of Compound 2-1-207
在一單頸圓底燒瓶中，混合o-DCB (80 ml) 、化合物15-2 (10.0 g, 30.94 mmol) 、試劑(12.9 g, 34.04 mmol)、Cu (0.19 g, 3.09 mmol) 、18-冠-6-醚(1.0 g, 3.09 mmol) 及K2 CO3 (12.8 g, 92.82 mmol) 得到一混合物，將其回流並於氮氣環境下攪拌12小時。在減壓下蒸餾移除o-DCB，以管柱層析(SiO2 , 己烷 : MC = 3: 1)分離，得到白色固體化合物2-1-207 (12.2 g, 63%)。In a single neck round bottom flask, mix o-DCB (80 ml), compound 15-2 (10.0 g, 30.94 mmol), reagent (12.9 g, 34.04 mmol), Cu (0.19 g, 3.09 mmol), 18- A mixture of crown-6-ether (1.0 g, 3.09 mmol) and K 2 CO 3 (12.8 g, 92.82 mmol) was obtained, which was refluxed and stirred under nitrogen for 12 hours. Distilled under reduced pressure to remove o-DCB, by column chromatography (SiO 2, hexane: MC = 3: 1) was separated to give 2-1-207 (12.2 g, 63%) as a white solid compound.
＜ 製備例 42＞ 製備化合物 2-1-208 < Preparation Example 42> Preparation of Compound 2-1-208
利用與製備例41中製備化合物2-1-207的方法相同的方式，除了使用N-(二苯並[b,d]噻吩-2-基)二苯並[b,d]呋喃-2-胺取代方法中的雙(二苯並[b,d] 噻吩-2-基)胺，製備出一產物(12.4 g, 66%)。The same procedure as in the preparation of the compound 2-1-207 in Preparation 41 except that N-(dibenzo[b,d]thiophen-2-yl)dibenzo[b,d]furan-2- was used. A product (12.4 g, 66%) was prepared from the bis(dibenzo[b,d]thiophen-2-yl)amine in the amine substitution procedure.
＜ 製備例 43＞ 製備化合物 2-1-210 < Preparation Example 43> Preparation of Compound 2-1-210
利用與製備例41中製備化合物2-1-207的方法相同的方式，除了使用N-(9,9-二甲基-9H-芴-3-基)二苯並[b,d]呋喃-2-胺取代方法中的雙(二苯並[b,d] 噻吩-2-基)胺，製備出一產物(13.6 g, 71%)。The same procedure as in the preparation of the compound 2-1-207 in Preparation 41 except that N-(9,9-dimethyl-9H-indol-3-yl)dibenzo[b,d]furan- A product (13.6 g, 71%) was prepared from the bis(dibenzo[b,d]thiophen-2-yl)amine in the 2-amine substitution procedure.
＜ 製備例 44＞ 製備化合物 2-1-213 < Preparation Example 44> Preparation of Compound 2-1-213
利用與製備例41中製備化合物2-1-207的方法相同的方式，除了使用N-(9,9'-螺二[芴]-2-基)二苯並[b,d]呋喃-2-胺取代方法中的雙(二苯並[b,d] 噻吩-2-基)胺，製備出一產物(12.1 g, 53%)。The same procedure as in the preparation of the compound 2-1-207 in Preparation 41 except that N-(9,9'-spirobis[芴]-2-yl)dibenzo[b,d]furan-2 was used. - A bis(dibenzo[b,d]thiophen-2-yl)amine in the amine substitution process to give a product (12.1 g, 53%).
化合物2-1-1至化合物2-1-216可基於製備例23至44，經由修改鍵結的取代基而製備出來。Compound 2-1-1 to compound 2-1-216 can be prepared based on Preparation Examples 23 to 44 by modifying the bonded substituent.
如同與製備例中的相同方式製備出化合物，且其合成之確認結果顯於於表3及表4。表3係關於1 H NMR (CDCl3 , 200 Mz)的測量值，且表2係關於場退吸質譜儀 (FD-MS) 的測量值。The compound was prepared in the same manner as in the preparation example, and the results of the synthesis were confirmed in Tables 3 and 4. Table 3 is a measure of 1 H NMR (CDCl 3 , 200 Mz), and Table 2 is a measurement of the field desorption mass spectrometer (FD-MS).
＜< 實驗例Experimental example ＞> 製造有機電致發光裝置Manufacturing organic electroluminescent device
＜< 比較例Comparative example 1＞1>
取一玻璃基板，其具有1,500 Å 厚度之ITO薄層，以二次水進行超音波清洗。當二次水清洗完成，以如丙酮、甲醇、及異丙醇之溶劑進行超音波清洗，乾燥後，利用UV光於UV清潔機中進行uvo處理5分鐘。之後，將基板移至電漿清潔機(PT)中，然後於真空狀態進行用於ITO功函數之電漿處理，且為了移除剩餘膜，因而移至用於有機沉積之熱沉積設備。A glass substrate having a thin layer of 1,500 Å thick ITO was used for ultrasonic cleaning with secondary water. When the secondary water cleaning is completed, ultrasonic cleaning is performed with a solvent such as acetone, methanol, and isopropyl alcohol, and after drying, UV treatment is performed in a UV cleaner for 5 minutes. Thereafter, the substrate was transferred to a plasma cleaner (PT), and then plasma treatment for the ITO work function was performed in a vacuum state, and in order to remove the remaining film, it was moved to a thermal deposition apparatus for organic deposition.
於上述製備的ITO透明電極(正極)上，藉由真空熱沉積N,N'-雙(α-萘基)-N,N'-二苯基-4,4'-二胺 (NPB) ，使其具有400 Å的厚度，以形成電洞傳輸層。On the ITO transparent electrode (positive electrode) prepared above, N,N'-bis(α-naphthyl)-N,N'-diphenyl-4,4'-diamine (NPB) was thermally deposited by vacuum, It is made to have a thickness of 400 Å to form a hole transport layer.
形成共用的電洞注入層及電洞傳輸層，然後於其上真空熱沉積一發光層，如下述。沉積的發光層具有200 Å 的厚度，利用4,4'-N,N'-二咔唑聯苯(CBP)作為主體，以及Ir(ppy)3 作為綠磷光摻雜劑，以使CBP摻雜Ir(ppy)3 (濃度7%)。之後，沉積 2,9-二甲基-4,7-二苯基-1,10-菲羅啉(BCP)，使其具有60 Å之厚度，作為電洞阻擋層，並於其上沉積三（8-羥基喹啉）鋁 (Alq3 ) ，使其具有200 Å之厚度，作為電子傳輸層。最後，於電子傳輸層上沉積氟化鋰(LiF) ，使其具有10 Å之厚度，作為電子注入層，然後於電子注入層上沉積厚度1,200 Å之鋁(Al)負極，製造出有機電致發光裝置。A common hole injection layer and a hole transport layer are formed, and then a light-emitting layer is vacuum-deposited thereon as described below. The deposited luminescent layer has a thickness of 200 Å, using 4,4'-N, N'-dicarbazole biphenyl (CBP) as a host, and Ir(ppy) 3 as a green phosphorescent dopant to dope CBP Ir(ppy) 3 (concentration 7%). Thereafter, 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline (BCP) was deposited to have a thickness of 60 Å as a hole barrier and three deposited thereon. (8-Hydroxyquinoline) aluminum (Alq 3 ) having a thickness of 200 Å as an electron transport layer. Finally, lithium fluoride (LiF) was deposited on the electron transport layer to have a thickness of 10 Å as an electron injection layer, and then an aluminum (Al) negative electrode having a thickness of 1,200 Å was deposited on the electron injection layer to produce an organic electro-electrode. Light emitting device.
並且，製造OLED裝置所需的所有有機化合物，皆在10-6 至10-8 torr下進行真空昇華純化(vacuum sublimed purification)，並用於製造OLED。Moreover, all of the organic compounds required for the fabrication of OLED devices are vacuum sublimed purification at 10 -6 to 10 -8 torr and are used to fabricate OLEDs.
＜< 實施例Example 1＞1>
利用與比較例1相同的方式，除了在比較例1中形成電子傳輸層時，使用化合物1-1-18取代Alq3 ，製造出有機電致發光裝置。In the same manner as in Comparative Example 1, except that the electron transport layer was formed in Comparative Example 1, the compound 1-1-18 was used instead of Alq 3 to produce an organic electroluminescence device.
＜< 實施例Example 2＞2>
利用與比較例1相同的方式，除了在比較例1中形成電子傳輸層時，使用化合物1-1-20取代Alq3 ，製造出有機電致發光裝置。In the same manner as in Comparative Example 1, except that the electron transport layer was formed in Comparative Example 1, the compound 1-1-20 was used instead of Alq 3 to produce an organic electroluminescence device.
＜< 實施例Example 3＞3>
利用與比較例1相同的方式，除了在比較例1中形成電子傳輸層時，使用化合物1-1-27取代Alq3 ，製造出有機電致發光裝置。In the same manner as in Comparative Example 1, except that the electron transport layer was formed in Comparative Example 1, the compound 1-1-27 was used instead of Alq 3 to produce an organic electroluminescence device.
＜< 實施例Example 4＞4>
利用與比較例1相同的方式，除了在比較例1中形成電子傳輸層時，使用化合物1-1-37取代Alq3 ，製造出有機電致發光裝置。In the same manner as in Comparative Example 1, except that the electron transport layer was formed in Comparative Example 1, the compound 1-1-37 was used instead of Alq 3 to produce an organic electroluminescence device.
＜< 實施例Example 5＞5>
利用與比較例1相同的方式，除了在比較例1中形成電子傳輸層時，使用化合物1-1-38取代Alq3 ，製造出有機電致發光裝置。In the same manner as in Comparative Example 1, except that the electron transport layer was formed in Comparative Example 1, the organic electroluminescent device was produced by using the compound 1-1-38 instead of Alq 3 .
＜< 實施例Example 6＞6>
利用與比較例1相同的方式，除了在比較例1中形成電子傳輸層時，使用化合物1-1-63取代Alq3 ，製造出有機電致發光裝置。In the same manner as in Comparative Example 1, except that the electron transport layer was formed in Comparative Example 1, the compound 1-1-63 was used instead of Alq 3 to produce an organic electroluminescence device.
＜< 實施例Example 7＞7>
利用與比較例1相同的方式，除了在比較例1中形成電子傳輸層時，使用化合物1-1-66取代Alq3 ，製造出有機電致發光裝置。In the same manner as in Comparative Example 1, except that the electron transport layer was formed in Comparative Example 1, the compound 1-1-66 was used instead of Alq 3 to produce an organic electroluminescence device.
＜< 實施例Example 8＞8>
利用與比較例1相同的方式，除了在比較例1中形成電子傳輸層時，使用化合物1-1-97取代Alq3 ，製造出有機電致發光裝置。In the same manner as in Comparative Example 1, except that the electron transport layer was formed in Comparative Example 1, the compound 1-1-97 was used instead of Alq 3 to produce an organic electroluminescence device.
＜< 實施例Example 9＞9>
利用與比較例1相同的方式，除了在比較例1中形成電子傳輸層時，使用化合物1-1-102取代Alq3 ，製造出有機電致發光裝置。In the same manner as in Comparative Example 1, except that the electron transport layer was formed in Comparative Example 1, the compound 1-1-102 was used instead of Alq 3 to produce an organic electroluminescence device.
＜< 實施例Example 10＞10>
利用與比較例1相同的方式，除了在比較例1中形成電子傳輸層時，使用化合物1-1-109取代Alq3 ，製造出有機電致發光裝置。In the same manner as in Comparative Example 1, except that the electron transport layer was formed in Comparative Example 1, the compound 1-1-109 was used instead of Alq 3 to produce an organic electroluminescence device.
＜< 實施例Example 11＞11>
利用與比較例1相同的方式，除了在比較例1中形成電子傳輸層時，使用化合物1-1-154取代Alq3 ，製造出有機電致發光裝置。In the same manner as in Comparative Example 1, except that the electron transport layer was formed in Comparative Example 1, the compound 1-1-154 was used instead of Alq 3 to produce an organic electroluminescence device.
＜< 實施例Example 12＞12>
利用與比較例1相同的方式，除了在比較例1中形成電子傳輸層時，使用化合物1-1-155取代Alq3 ，製造出有機電致發光裝置。In the same manner as in Comparative Example 1, except that the electron transport layer was formed in Comparative Example 1, the compound 1-1-155 was used instead of Alq 3 to produce an organic electroluminescence device.
＜< 實施例Example 13＞13>
利用與比較例1相同的方式，除了在比較例1中形成電子傳輸層時，使用化合物1-1-156取代Alq3 ，製造出有機電致發光裝置。In the same manner as in Comparative Example 1, except that the electron transport layer was formed in Comparative Example 1, the compound 1-1-156 was used instead of Alq 3 to produce an organic electroluminescence device.
＜< 實施例Example 14＞14>
利用與比較例1相同的方式，除了在比較例1中形成電子傳輸層時，使用化合物1-1-166取代Alq3 ，製造出有機電致發光裝置。In the same manner as in Comparative Example 1, except that the electron transport layer was formed in Comparative Example 1, the compound 1-1-166 was used instead of Alq 3 to produce an organic electroluminescence device.
＜< 實施例Example 15＞15>
利用與比較例1相同的方式，除了在比較例1中形成電子傳輸層時，使用化合物1-1-167取代Alq3 ，製造出有機電致發光裝置。In the same manner as in Comparative Example 1, except that the electron transport layer was formed in Comparative Example 1, the compound 1-1-167 was used instead of Alq 3 to produce an organic electroluminescence device.
＜< 實施例Example 16＞16>
利用與比較例1相同的方式，除了在比較例1中形成電子傳輸層時，使用化合物1-1-186取代Alq3 ，製造出有機電致發光裝置。In the same manner as in Comparative Example 1, except that the electron transport layer was formed in Comparative Example 1, the compound 1-1-186 was used instead of Alq 3 to produce an organic electroluminescence device.
＜< 實施例Example 17＞17>
利用與比較例1相同的方式，除了在比較例1中形成電子傳輸層時，使用化合物1-1-192取代Alq3 ，製造出有機電致發光裝置。In the same manner as in Comparative Example 1, except that the electron transport layer was formed in Comparative Example 1, the compound 1-1-192 was used instead of Alq 3 to produce an organic electroluminescence device.
＜< 實施例Example 18＞18>
利用與比較例1相同的方式，除了在比較例1中形成電子傳輸層時，使用化合物1-1-193取代Alq3 ，製造出有機電致發光裝置。In the same manner as in Comparative Example 1, except that the electron transport layer was formed in Comparative Example 1, the organic electroluminescent device was produced by using the compound 1-1-193 instead of Alq 3 .
＜< 實施例Example 19＞19>
利用與比較例1相同的方式，除了在比較例1中形成發光層時，使用化合物1-1-86取代CBP，製造出有機電致發光裝置。In the same manner as in Comparative Example 1, except that the light-emitting layer was formed in Comparative Example 1, the compound 1-1-86 was used instead of CBP to produce an organic electroluminescence device.
＜< 實施例Example 20＞20>
利用與比較例1相同的方式，除了在比較例1中形成發光層時，使用化合物1-1-180取代CBP，製造出有機電致發光裝置。In the same manner as in Comparative Example 1, except that the light-emitting layer was formed in Comparative Example 1, the organic electroluminescent device was produced by using the compound 1-1-180 instead of CBP.
＜< 實施例Example 21＞21>
利用與比較例1相同的方式，除了在比較例1中形成發光層時，使用化合物1-1-120取代CBP，製造出有機電致發光裝置。In the same manner as in Comparative Example 1, except that the light-emitting layer was formed in Comparative Example 1, the compound 1-1-120 was used instead of CBP to produce an organic electroluminescence device.
＜< 實施例Example 22＞22>
利用與比較例1相同的方式，除了在比較例1中形成發光層時，使用化合物1-1-190取代CBP，製造出有機電致發光裝置。In the same manner as in Comparative Example 1, except that the light-emitting layer was formed in Comparative Example 1, the compound 1-1-190 was used instead of CBP to produce an organic electroluminescence device.
＜< 實施例Example 23twenty three 至to 42＞42>
利用與比較例1相同的方式，除了在比較例1中形成電洞傳輸層時，使用化合物1-1-197至化合物1-1-216中任一個取代NPB，製造出有機電致發光裝置。In the same manner as in Comparative Example 1, except that the hole transport layer was formed in Comparative Example 1, the organic electroluminescent device was produced by substituting NPB with any of the compounds 1-1-197 to 1-1-216.
＜< 實施例Example 43＞43>
利用與比較例1相同的方式，除了在比較例1中形成電子傳輸層時，使用化合物2-1-18取代Alq3 ，製造出有機電致發光裝置。In the same manner as in Comparative Example 1, except that the electron transport layer was formed in Comparative Example 1, the compound 2-1-18 was used instead of Alq 3 to produce an organic electroluminescence device.
＜< 實施例Example 44＞44>
利用與比較例1相同的方式，除了在比較例1中形成電子傳輸層時，使用化合物2-1-20取代Alq3 ，製造出有機電致發光裝置。In the same manner as in Comparative Example 1, except that the electron transport layer was formed in Comparative Example 1, the compound 2-1-20 was used instead of Alq 3 to produce an organic electroluminescence device.
＜< 實施例Example 45＞45>
利用與比較例1相同的方式，除了在比較例1中形成電子傳輸層時，使用化合物2-1-27取代Alq3 ，製造出有機電致發光裝置。In the same manner as in Comparative Example 1, except that the electron transport layer was formed in Comparative Example 1, the compound 2-1-27 was used instead of Alq 3 to produce an organic electroluminescence device.
＜< 實施例Example 46＞46>
利用與比較例1相同的方式，除了在比較例1中形成電子傳輸層時，使用化合物2-1-37取代Alq3 ，製造出有機電致發光裝置。In the same manner as in Comparative Example 1, except that the electron transport layer was formed in Comparative Example 1, the compound 2-1-37 was used instead of Alq 3 to produce an organic electroluminescence device.
＜< 實施例Example 47＞47>
利用與比較例1相同的方式，除了在比較例1中形成電子傳輸層時，使用化合物2-1-38取代Alq3 ，製造出有機電致發光裝置。In the same manner as in Comparative Example 1, except that the electron transport layer was formed in Comparative Example 1, the compound 2-1-38 was used instead of Alq 3 to produce an organic electroluminescence device.
＜< 實施例Example 48＞48>
利用與比較例1相同的方式，除了在比較例1中形成電子傳輸層時，使用化合物2-1-63取代Alq3 ，製造出有機電致發光裝置。In the same manner as in Comparative Example 1, except that the electron transport layer was formed in Comparative Example 1, the compound 2-1-63 was used instead of Alq 3 to produce an organic electroluminescence device.
＜< 實施例Example 49＞49>
利用與比較例1相同的方式，除了在比較例1中形成電子傳輸層時，使用化合物2-1-66取代Alq3 ，製造出有機電致發光裝置。In the same manner as in Comparative Example 1, except that the electron transport layer was formed in Comparative Example 1, the compound 2-1-66 was used instead of Alq 3 to produce an organic electroluminescence device.
＜< 實施例Example 50＞50>
利用與比較例1相同的方式，除了在比較例1中形成電子傳輸層時，使用化合物2-1-86取代Alq3 ，製造出有機電致發光裝置。In the same manner as in Comparative Example 1, except that the electron transport layer was formed in Comparative Example 1, the compound 2-1-86 was used instead of Alq 3 to produce an organic electroluminescence device.
＜< 實施例Example 51＞51>
利用與比較例1相同的方式，除了在比較例1中形成電子傳輸層時，使用化合物2-1-97取代Alq3 ，製造出有機電致發光裝置。In the same manner as in Comparative Example 1, except that the electron transport layer was formed in Comparative Example 1, the compound 2-1-97 was used instead of Alq 3 to produce an organic electroluminescence device.
＜< 實施例Example 52＞52>
利用與比較例1相同的方式，除了在比較例1中形成電子傳輸層時，使用化合物2-1-102取代Alq3 ，製造出有機電致發光裝置。In the same manner as in Comparative Example 1, except that the electron transport layer was formed in Comparative Example 1, the compound 2-1-102 was used instead of Alq 3 to produce an organic electroluminescence device.
＜< 實施例Example 53＞53>
利用與比較例1相同的方式，除了在比較例1中形成電子傳輸層時，使用化合物2-1-109取代Alq3 ，製造出有機電致發光裝置。In the same manner as in Comparative Example 1, except that the electron transport layer was formed in Comparative Example 1, the compound 2-1-109 was used instead of Alq 3 to produce an organic electroluminescence device.
＜< 實施例Example 54＞54>
利用與比較例1相同的方式，除了在比較例1中形成電子傳輸層時，使用化合物2-1-120取代Alq3 ，製造出有機電致發光裝置。In the same manner as in Comparative Example 1, except that the electron transport layer was formed in Comparative Example 1, the compound 2-1-120 was used instead of Alq 3 to produce an organic electroluminescence device.
＜< 實施例Example 55＞55>
利用與比較例1相同的方式，除了在比較例1中形成電子傳輸層時，使用化合物2-1-154取代Alq3 ，製造出有機電致發光裝置。In the same manner as in Comparative Example 1, except that the electron transport layer was formed in Comparative Example 1, the compound 2-1-154 was used instead of Alq 3 to produce an organic electroluminescence device.
＜< 實施例Example 56＞56>
利用與比較例1相同的方式，除了在比較例1中形成電子傳輸層時，使用化合物2-1-155取代Alq3 ，製造出有機電致發光裝置。By the same manner as in Comparative Example 1, except that when forming the electron transport layer in Comparative Example 1, using Compound 2-1-155 substituted Alq 3, thereby making an organic electroluminescent device.
＜< 實施例Example 57＞57>
利用與比較例1相同的方式，除了在比較例1中形成電子傳輸層時，使用化合物2-1-156取代Alq3 ，製造出有機電致發光裝置。In the same manner as in Comparative Example 1, except that the electron transport layer was formed in Comparative Example 1, the compound 2-1-156 was used instead of Alq 3 to produce an organic electroluminescence device.
＜< 實施例Example 58＞58>
利用與比較例1相同的方式，除了在比較例1中形成電子傳輸層時，使用化合物2-1-166取代Alq3 ，製造出有機電致發光裝置。In the same manner as in Comparative Example 1, except that the electron transport layer was formed in Comparative Example 1, the compound 2-1-166 was used instead of Alq 3 to produce an organic electroluminescence device.
＜< 實施例Example 59＞59>
利用與比較例1相同的方式，除了在比較例1中形成電子傳輸層時，使用化合物2-1-167取代Alq3 ，製造出有機電致發光裝置。In the same manner as in Comparative Example 1, except that the electron transport layer was formed in Comparative Example 1, the compound 2-1-167 was used instead of Alq 3 to produce an organic electroluminescence device.
＜< 實施例Example 60＞60>
利用與比較例1相同的方式，除了在比較例1中形成電子傳輸層時，使用化合物2-1-180取代Alq3 ，製造出有機電致發光裝置。In the same manner as in Comparative Example 1, except that the electron transport layer was formed in Comparative Example 1, the compound 2-1-180 was used instead of Alq 3 to produce an organic electroluminescence device.
＜< 實施例Example 61＞61>
利用與比較例1相同的方式，除了在比較例1中形成電子傳輸層時，使用化合物2-1-186取代Alq3 ，製造出有機電致發光裝置。In the same manner as in Comparative Example 1, except that the electron transport layer was formed in Comparative Example 1, the compound 2-1-186 was used instead of Alq 3 to produce an organic electroluminescence device.
＜< 實施例Example 62＞62>
利用與比較例1相同的方式，除了在比較例1中形成電子傳輸層時，使用化合物2-1-190取代Alq3 ，製造出有機電致發光裝置。In the same manner as in Comparative Example 1, except that the electron transport layer was formed in Comparative Example 1, the compound 2-1-190 was used instead of Alq 3 to produce an organic electroluminescence device.
＜< 實施例Example 63＞63>
利用與比較例1相同的方式，除了在比較例1中形成電子傳輸層時，使用化合物2-1-192取代Alq3 ，製造出有機電致發光裝置。In the same manner as in Comparative Example 1, except that the electron transport layer was formed in Comparative Example 1, the compound 2-1-192 was used instead of Alq 3 to produce an organic electroluminescence device.
＜< 實施例Example 64＞64>
利用與比較例1相同的方式，除了在比較例1中形成電子傳輸層時，使用化合物2-1-193取代Alq3 ，製造出有機電致發光裝置。In the same manner as in Comparative Example 1, except that the electron transport layer was formed in Comparative Example 1, the compound 2-1-193 was used instead of Alq 3 to produce an organic electroluminescence device.
＜< 實施例Example 6565 至to 84＞84>
利用與比較例1相同的方式，除了在比較例1中形成電洞傳輸層時，使用化合物2-1-197至化合物2-1-216中任一個取代NPB，製造出有機電致發光裝置。In the same manner as in Comparative Example 1, except that the hole transport layer was formed in Comparative Example 1, the NPB was replaced with any one of the compounds 2-1-197 to 2-1-216 to produce an organic electroluminescence device.
＜< 實驗例Experimental example 1＞1> 有機電致發光裝置之驅動電壓、發光效率及使用壽命Driving voltage, luminous efficiency and service life of organic electroluminescent devices
針對比較例1及實施例1至18中製造的有機電致發光裝置，當發光亮度為1,000 cd/m2 時，測量驅動電壓及發光效率，且根據裝置於2,000 cd/m2 所經過的驅動時間，測量當亮度下降至初始驅動時亮度的90%時所花費的時間做為使用壽命，結果顯示於下表5。With respect to the organic electroluminescence device manufactured in Comparative Example 1 and Examples 1 to 18, when the luminance of the emitted light was 1,000 cd/m 2 , the driving voltage and the luminous efficiency were measured, and the driving was performed according to the device at 2,000 cd/m 2 . Time, the time taken when the brightness dropped to 90% of the brightness at the initial driving was measured as the service life, and the results are shown in Table 5 below.
在此例中，利用McScience Inc.製造的IVL量測儀(M7000)測量電致發光 (EL) 特性，以測量發光效率。利用McScience Inc.製造的M6000PMX於參考亮度時300 cd/m2 測量T90之使用壽命。In this example, electroluminescence (EL) characteristics were measured using an IVL measuring instrument (M7000) manufactured by McScience Inc. to measure luminous efficiency. The lifetime of the T90 was measured using a M6000PMX manufactured by McScience Inc. at a reference luminance of 300 cd/m 2 .
如實驗結果，可證實實施例1至18使用本發明化合物製造之有機電致發光裝置相較於比較例1使用習知Alq3 之有機電致發光裝置具有較低的驅動電壓、較高的發光效率、及較佳的使用壽命性質。As a result of the experiment, it was confirmed that the organic electroluminescent devices of Examples 1 to 18 using the compound of the present invention have lower driving voltage and higher luminescence than the organic electroluminescent device of Comparative Example 1 using the conventional Alq 3 . Efficiency, and better service life properties.
因此，當使用本發明之化合物作為有機電致發光裝置中電子傳輸層之材料時，由於核心結構中兩個N的位置相鄰，電子傳輸能力優異且可改善驅動電壓。此外，由於根據化合物之低HOMO值之電洞阻擋功能，從發光層轉移至包含本發明化合物之層的電洞數目減少，因而可提升其發光效率及使用壽命。Therefore, when the compound of the present invention is used as a material of the electron transport layer in the organic electroluminescence device, since the positions of the two Ns in the core structure are adjacent, the electron transport ability is excellent and the driving voltage can be improved. Further, since the number of holes transferred from the light-emitting layer to the layer containing the compound of the present invention is reduced in accordance with the hole blocking function of the low HOMO value of the compound, the luminous efficiency and the service life thereof can be improved.
＜< 實驗例Experimental example 2＞2> 有機電致發光裝置之驅動電壓、發光效率及使用壽命Driving voltage, luminous efficiency and service life of organic electroluminescent devices
針對比較例1及實施例19至22中製造的有機電致發光裝置，當發光亮度為1,000 cd/m2 時，測量驅動電壓及發光效率，且根據裝置於2,000 cd/m2 所經過的驅動時間，測量當亮度下降至初始驅動時亮度的90%時所花費的時間做為使用壽命，結果顯示於下表6。With respect to the organic electroluminescence device manufactured in Comparative Example 1 and Examples 19 to 22, when the luminance of the emitted light was 1,000 cd/m 2 , the driving voltage and the luminous efficiency were measured, and the driving was performed according to the device at 2,000 cd/m 2 . Time, the time taken when the brightness dropped to 90% of the brightness at the initial driving was measured as the service life, and the results are shown in Table 6 below.
在此例中，利用McScience Inc.製造的IVL量測儀(M7000)測量電致發光 (EL) 特性，以測量發光效率。利用McScience Inc.製造的M6000PMX於參考亮度時300 cd/m2 測量T90之使用壽命。In this example, electroluminescence (EL) characteristics were measured using an IVL measuring instrument (M7000) manufactured by McScience Inc. to measure luminous efficiency. The lifetime of the T90 was measured using a M6000PMX manufactured by McScience Inc. at a reference luminance of 300 cd/m 2 .
如實驗結果，可證實實施例19至22使用本發明化合物製造之有機電致發光裝置相較於比較例1使用習知CBP之有機電致發光裝置具有較低的驅動電壓、較高的發光效率、及較佳的使用壽命性質。As a result of the experiment, it was confirmed that the organic electroluminescent devices manufactured by using the compounds of the present invention in Examples 19 to 22 have lower driving voltage and higher luminous efficiency than the organic electroluminescent device using the conventional CBP as compared with Comparative Example 1. And better service life properties.
換言之，由於根據本發明化合物的結構包含電子傳輸基團及電洞傳輸基團，故能夠妥善維持化合物的電洞遷移率及電子遷移率，降低驅動電壓並提升其發光效率及使用壽命。In other words, since the structure of the compound according to the present invention contains an electron transporting group and a hole transporting group, the hole mobility and electron mobility of the compound can be properly maintained, the driving voltage can be lowered, and the luminous efficiency and the service life can be improved.
＜< 實驗例Experimental example 3＞3> 有機電致發光裝置之驅動電壓、發光效率及使用壽命Driving voltage, luminous efficiency and service life of organic electroluminescent devices
針對比較例1及實施例23至42中製造的有機電致發光裝置，當發光亮度為1,000 cd/m2 時，測量驅動電壓及發光效率，且根據裝置於2,000 cd/m2 所經過的驅動時間，測量當亮度下降至初始驅動時亮度的90%時所花費的時間做為使用壽命，結果顯示於下表7。With respect to the organic electroluminescence device manufactured in Comparative Example 1 and Examples 23 to 42, when the luminance of the emitted light was 1,000 cd/m 2 , the driving voltage and the luminous efficiency were measured, and the driving was performed according to the device at 2,000 cd/m 2 . Time, the time taken when the brightness dropped to 90% of the brightness at the initial driving was measured as the service life, and the results are shown in Table 7 below.
在此例中，利用McScience Inc.製造的IVL量測儀(M7000)測量電致發光 (EL) 特性，以測量發光效率。利用McScience Inc.製造的M6000PMX於參考亮度時300 cd/m2 測量T90之使用壽命。In this example, electroluminescence (EL) characteristics were measured using an IVL measuring instrument (M7000) manufactured by McScience Inc. to measure luminous efficiency. The lifetime of the T90 was measured using a M6000PMX manufactured by McScience Inc. at a reference luminance of 300 cd/m 2 .
[表7]
如實驗結果，可證實實施例23至42使用本發明化合物製造之有機電致發光裝置相較於比較例1使用習知NPB之有機電致發光裝置具有較低的驅動電壓、較高的發光效率、及較佳的使用壽命性質。As a result of the experiment, it was confirmed that the organic electroluminescent devices of Examples 23 to 42 using the compound of the present invention have lower driving voltage and higher luminous efficiency than the organic electroluminescent device of Comparative Example 1 using the conventional NPB. And better service life properties.
＜< 實驗例Experimental example 4＞4> 有機電致發光裝置之驅動電壓、發光效率及使用壽命Driving voltage, luminous efficiency and service life of organic electroluminescent devices
針對比較例1及實施例43至64中製造的有機電致發光裝置，當發光亮度為1,000 cd/m2 時，測量驅動電壓及發光效率，且根據裝置於2,000 cd/m2 所經過的驅動時間，測量當亮度下降至初始驅動時亮度的90%時所花費的時間做為使用壽命，結果顯示於下表8。With respect to the organic electroluminescence device manufactured in Comparative Example 1 and Examples 43 to 64, when the luminance of the emitted light was 1,000 cd/m 2 , the driving voltage and the luminous efficiency were measured, and the driving was performed according to the device at 2,000 cd/m 2 . Time, the time taken when the brightness dropped to 90% of the brightness at the initial driving was measured as the service life, and the results are shown in Table 8 below.
在此例中，利用McScience Inc.製造的IVL量測儀(M7000)測量電致發光 (EL) 特性，以測量發光效率。利用McScience Inc.製造的M6000PMX於參考亮度時300 cd/m2 測量T90之使用壽命。In this example, electroluminescence (EL) characteristics were measured using an IVL measuring instrument (M7000) manufactured by McScience Inc. to measure luminous efficiency. The lifetime of the T90 was measured using a M6000PMX manufactured by McScience Inc. at a reference luminance of 300 cd/m 2 .
如實驗結果，可證實實施例43至64使用本發明化合物製造之有機電致發光裝置相較於比較例1使用習知Alq3 之有機電致發光裝置具有較低的驅動電壓、較高的發光效率、及較佳的使用壽命性質。As a result of the experiment, it was confirmed that the organic electroluminescent devices of Examples 43 to 64 using the compound of the present invention have lower driving voltage and higher luminescence than the organic electroluminescent device of Comparative Example 1 using the conventional Alq 3 . Efficiency, and better service life properties.
因此，當使用本發明之化合物作為有機電致發光裝置中電子傳輸層之材料時，由於核心結構中兩個N的位置相鄰，電子傳輸能力優異且可改善驅動電壓。此外，由於根據化合物之低HOMO值之電洞阻擋功能，從發光層轉移至包含本發明化合物之層的電洞數目減少，因而可提升其發光效率及使用壽命。Therefore, when the compound of the present invention is used as a material of the electron transport layer in the organic electroluminescence device, since the positions of the two Ns in the core structure are adjacent, the electron transport ability is excellent and the driving voltage can be improved. Further, since the number of holes transferred from the light-emitting layer to the layer containing the compound of the present invention is reduced in accordance with the hole blocking function of the low HOMO value of the compound, the luminous efficiency and the service life thereof can be improved.
＜< 實驗例Experimental example 5＞5> 有機電致發光裝置之驅動電壓、發光效率及使用壽命Driving voltage, luminous efficiency and service life of organic electroluminescent devices
針對比較例1及實施例65至84中製造的有機電致發光裝置，當發光亮度為1,000 cd/m2 時，測量驅動電壓及發光效率，且根據裝置於2,000 cd/m2 所經過的驅動時間，測量當亮度下降至初始驅動時亮度的90%時所花費的時間做為使用壽命，結果顯示於下表9。With respect to the organic electroluminescence device manufactured in Comparative Example 1 and Examples 65 to 84, when the luminance of the emitted light was 1,000 cd/m 2 , the driving voltage and the luminous efficiency were measured, and the driving was performed according to the device at 2,000 cd/m 2 . Time, the time taken when the brightness dropped to 90% of the brightness at the initial driving was measured as the service life, and the results are shown in Table 9 below.
在此例中，利用McScience Inc.製造的IVL量測儀(M7000)測量電致發光 (EL) 特性，以測量發光效率。利用McScience Inc.製造的M6000PMX於參考亮度時300 cd/m2 測量T90之使用壽命。In this example, electroluminescence (EL) characteristics were measured using an IVL measuring instrument (M7000) manufactured by McScience Inc. to measure luminous efficiency. The lifetime of the T90 was measured using a M6000PMX manufactured by McScience Inc. at a reference luminance of 300 cd/m 2 .
如實驗結果，可證實實施例65至84使用本發明化合物製造之有機電致發光裝置相較於比較例1使用習知NPB之有機電致發光裝置具有較低的驅動電壓、較高的發光效率、及較佳的使用壽命性質。As a result of the experiment, it can be confirmed that the organic electroluminescent devices manufactured by using the compounds of the present invention in Examples 65 to 84 have lower driving voltage and higher luminous efficiency than the organic electroluminescent device using the conventional NPB in Comparative Example 1. And better service life properties.
以上描述本發明之較佳實施例，但本發明並未受限於此，在申請專利範圍及詳細說明之範疇內，該些實施例自然可做各種變化，且該些變化亦落入本發明之範疇中。The preferred embodiments of the present invention are described above, but the present invention is not limited thereto, and various modifications can be made in the embodiments within the scope of the claims and the detailed description, and the modifications are also included in the present invention. In the category.
100‧‧‧基板
200‧‧‧正極
300‧‧‧有機材料層
301‧‧‧電洞注入層
302‧‧‧電洞傳輸層
303‧‧‧發光層
304‧‧‧電洞阻擋層
305‧‧‧電子傳輸層
306‧‧‧電子注入層
400‧‧‧負極100‧‧‧Substrate
200‧‧‧ positive
300‧‧‧ organic material layer
301‧‧‧ hole injection layer
302‧‧‧ hole transport layer
303‧‧‧Lighting layer
304‧‧‧ hole barrier
305‧‧‧Electronic transport layer
306‧‧‧Electronic injection layer
400‧‧‧negative
圖1至圖3分別為本發明實施例之有機發光裝置之堆疊結構示意圖。1 to 3 are schematic diagrams showing a stack structure of an organic light-emitting device according to an embodiment of the present invention.
100‧‧‧基板 100‧‧‧Substrate
200‧‧‧正極 200‧‧‧ positive
300‧‧‧有機材料層 300‧‧‧ organic material layer
400‧‧‧負極 400‧‧‧negative
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